Diarylethene compounds and uses thereof

ABSTRACT

A compound according to Formula IA and IB, reversibly convertible under photochromic and electrochromic conditions between a ring-open isomer A and a ring-closed isomer B is provided. For substitutent groups, Z is N, O or S; each R 1  is independently selected from the group consisting of H, or halo; each R 2  is independently selected from the group consisting of H, halo, a polymer backbone, alkyl or aryl; or, when both R 2  together form —CH═CH— and form part of a polymer backbone; each R 3  is independently selected from the group consisting of H, halo, alkyl, alkoxy, thioalkyl or aryl; each R 4  is aryl; and each R 5  is independently selected from the group consisting of H, halo, alkyl, alkoxy, thioalkyl or aryl.

This application is a National Stage Application of PCT/CA2012/000910,filed 28 Sep. 2012, which claims the benefit of U.S. ProvisionalApplication No. 61/541,841 filed Sep. 30, 2011, and U.S. ProvisionalApplication No. 61/675,460 filed Jul. 25, 2012, both of which areincorporated herein by reference in their entirety. To the extentappropriate, a claim of priority is made to each of the above disclosedapplications.

FIELD OF THE INVENTION

The present invention relates to diarylethene compounds and usesthereof. More specifically, the compounds are reversibly convertiblebetween ring-open and ring-closed isomers.

BACKGROUND OF THE INVENTION

Photochromic molecules are useful for a variety of research andcommercial applications in fields ranging from sunglasses to memorystorage devices. A myriad of configurations have been developed, seekingto obtain improvements in stability, control in switching, fatigueresistance, sensitivity and the like. Diarylethenes have found favourfor several of these traits, and are the subject of continuedinvestigation. A review by Irie (Proc. Jpn. Acad. Ser B 86:472-483,2010) illustrates a range in stability, colour and the like of selecteddiarylethenes.

PCT Publication WO2004/015024 describes compounds that are bothphotochromic and electrochromic, and methods of making such compounds,and describes a mechanism of catalytic electrochromism. Briefly, aring-closed form (isomer B) of a compound loses an electron underelectrochemical conditions, forming a radical cation. A rapidring-opening reaction occurs, providing the radical cation of isomer A,which oxidizes a neighbouring compound of isomer B, neutralizing theradical cation. This ring opening reaction may be initiated with a smallcharge, and perpetuates throughout the material, resulting in conversionof the ring-closed isomers to the ring-open isomers. PCT PublicationWO2010/142019 describes variable transmittance optical filterscomprising a material capable of transitioning between light and darkstates in response to ultraviolet light and electric voltage, thematerial comprising a chromophore that has both electrochromic andphotochromic properties.

Light transmission properties of such optical filters may be varied byselection of a photochromic-electrochromic diarylethene with greater orlesser light absorbance in the ring-open or ring-closed form. To providefor such variation, there is a need for molecules with improvedphotochromic, electrochromic or photochromic and electrochromicproperties.

SUMMARY OF THE INVENTION

There is a need for photochromic and electrochromic compounds withphotostationary states, or sensitivity index suitable for variousapplications. Such compounds may be useful as components of switchable,or dynamic, optical filters. The ability of a compound to absorb lightin the visible spectrum may be illustrated by the photostationary stateof the compound when exposed to full spectrum light. The problem ofneeding photochromic and electrochromic compounds that provide suitablelight absorption in a visible-light absorbing state may be solved bysynthesis of novel photochromic/electrochromic compounds demonstrating asuitable PSS, or a suitable sensitivity index.

The present disclosure relates to one or more compounds (“chromophores”)reversibly convertible between isomers. Conversion between isomers maybe light induced, or may occur under some oxidative conditions such aselectrochemical conditions, or a combination thereof.

In one aspect, there is provided a 1,2-diaryl cyclopentene compoundreversibly convertible between Formula 1A (ring-open isomer) and Formula1B (ring-closed isomer) of Scheme 1:

whereinZ may be N, O or S;Each R₁ may be independently selected from the group consisting of H,halo;Each R₂ may be independently selected from the group consisting of H,halo, a polymer backbone, alkyl or aryl; or, when both R₂ together form—CH═CH— and form part of a polymer backbone;Each R₃ may be independently selected from the group consisting of H,halo, CO₂Y, alkyl, alkoxy, carbonyl, thioalkyl, aryl,

—CH═CH—;and Y may be independently selected from the group comprising H, ametal, alkyl, aryl, —(O—CH₂CH₂)₄—H, or

Each R₄ may be independently selected from the group consisting of aryl,

Each R₅ may be independently selected from the group consisting of H,halo, alkyl, alkoxy, —CH═CH—, thioalkyl or aryl; and;Each X may independently be N, O or S:

R₄ may alternately be described as an “internal” group. R₃ mayalternately be described as an “external” group.

Each of R_(6a), R_(6b), R_(6c), R_(7a), R_(7b) and R_(7c) may beindependently selected from a group comprising one or more of H, halo,alkyl, alkoxy, carbonyl, siloxy, thioalkyl CO₂Y or aryl; and Y is asreferenced herein, with the proviso that at least one of R_(6a), R_(6b),R_(6c), and at least one of R_(7a), R_(7b) and R_(7c) are not H. TheR_(6a) and R_(7a) position may alternately be referred to as the “5position”; the R_(6b) and R_(7b) position may alternately be referred toas the “4 position”; the R_(6c) and R_(7c) position may alternately bereferred to as the “3 position” of the ring;

Each of R_(8a), R_(8b), R_(8c) R_(8d), R_(8e), R_(9a), R_(9b), R_(9c),R_(9d) and R_(9e) may be independently selected from the groupconsisting of H, halo, alkyl, alkoxy, thioalkyl, carbonyl, siloxy, arylor CO₂Y, and Y is as referenced herein, with the proviso that at leastone of R_(8a), R_(8b), R_(8c) R_(8d), or R_(8e), and at least one ofR_(9a), R_(9b), R_(9c), R_(9d) and R_(9e) are not H The R_(8c) andR_(9c) positions may alternately be referred to as a ‘para’ position;the R_(8b), R_(8d), R_(9b) and R_(9d) positions may alternately bereferred to as a ‘meta’ position; the R_(8a), R_(8e), R_(9a) and R_(9e)positions may alternately be referred to as an ‘ortho’ position.

In another aspect, R_(6a) and R_(6b), or R_(6b) and R_(6c) are each—CH═CH— and joined to form an unsaturated ring,

In another aspect, R_(7a) and R_(7b), or R_(7b) and R_(7c) are each—CH═CH— and joined to form an unsaturated ring.

In another aspect, R_(8a) and R_(8b), or R_(8b) and R_(8c), or R_(8c)and R_(8d), or R_(8d) and R_(8e) are each —CH═CH— and joined to form anunsaturated ring,

In another aspect, R_(9a) and R_(9b), or R_(9b) and R_(9c), or R_(9c)and R_(9d), or R_(9d) and R_(9e) are each —CH═CH— and joined to form anunsaturated ring.

In another aspect, R₃ is

and R₄ is

providing a compound reversibly convertible between Formula IIA(ring-open isomer) and Formula IIB (ring-closed isomer), and R_(6a) andR_(7a) are not methyl.

In another aspect, R₃ is

and R₄ is

providing a compound reversibly convertible between Formula IIIA(ring-open isomer) and Formula IIIB (ring-closed isomer) and R_(8c) andR_(9c) are not all —O—CH₃, or all —C(CH₃)₃

In another aspect, R₃ is

and R₄ is

providing a compound reversibly convertible between Formula IVA(ring-open isomer) and Formula IVB (ring-closed isomer) and R_(6a) isnot methyl

In another aspect, R₃ is

and R₄ is

providing a compound reversibly convertible between Formula VA(ring-open isomer) and Formula VB (ring-closed isomer) and R_(7a) is notmethyl.

In another aspect, a first R₃ group is

and a first R₄ group is

and a second R₃ group R₃′ is

and a second R₄ (R₄′) group is

providing a compound reversibly convertible between Formula VIA(ring-open isomer) and Formula VIB (ring-closed isomer) of Scheme 2:

In another aspect, a first R₃ and a first R₅ are each —CH═CH— and joinedto form an unsaturated ring, providing a group according to

providing a compound reversibly convertible between Formula XA(ring-open isomer) and Formula XB (ring-closed isomer) of Scheme 3:

Where Z is N, O or S;each R₁ is independently selected from the group consisting of H, orhalo;each R₂ is independently selected from the group consisting of H, halo,a polymer backbone, alkyl or aryl; or, when both R₂ together form—CH═CH— and form part of a polymer backbone;R₃ is —CH₂═CH₂—,

each R₄ is independently, aryl,

X is N, O or S;R₅ is independently selected from a group consisting of H, alkyl,alkoxy, —CH═CH—;each R_(6a), R_(6b), R_(6c) is independently selected from the groupconsisting of H, halo, alkyl, alkoxy, siloxy, thioalkyl or aryl;each R_(7a), R_(7b), R_(7c) is independently selected from the groupconsisting of H, halo, alkyl, alkoxy, siloxy, thioalkyl or aryl;each R_(8a), R_(8b), R_(8c), R_(8d), R_(8e) is independently selectedfrom the group consisting of H, halo, alkyl, alkoxy, siloxy, thioalkylor aryl;each R_(10a), R_(10b), R_(10c), R_(10d), is independently H, halo,alkyl, alkoxy, siloxy, thioalkyl or aryl, or any of R_(10a) and R_(10b),or R_(10b) and R_(10c), or R_(10c) R_(10d) are alkyl, or alkoxy, andjoined to form a 5 or 6 or 7 membered ring.

In another aspect, R₃ is

and R₄ is

providing a compound reversibly convertible between Formula VIIIA(ring-open isomer) and Formula VIIIB (ring-closed isomer).

In another aspect, R₃ is

and R₄ is

providing a compound reversibly convertible between Formula XIA(ring-open isomer) and Formula XIB (ring-closed isomer).

In another aspect, both R₃ and both R₅ are each —CH═CH— and joined toform an unsaturated ring, providing a compound reversibly convertiblebetween Formula VIIA (ring-open isomer) and Formula VIIB (ring-closedisomer) of Scheme 4:

In another aspect, R_(9c) may be an alkyl, alkoxy or siloxy group,selected from a group comprising an alkyl group comprising from one to20 carbons. In another aspect, one or more of R_(10a), R_(10b), R_(10c),R_(10d) may be an alkoxy or siloxy group, comprising from one to tenoxygen atoms and from one to 20 carbons. In another aspect, an R_(10b)and an R_(10c) are each O, and joined with a —CH₂— to form a 5 memberedring.

In another aspect, the compounds each comprise ring-open, or open,isomers (Isomer A) and ring-closed, or closed, isomers (Isomer B). Thesecompounds may be reversibly convertible between open and closed formsunder photochemical, oxidative, or photochemical and oxidativeconditions. Oxidative conditions may be electrochemical conditions.

In another aspect, the compounds may be convertible from the ring-openisomer A to the ring-closed isomer B under photochemical conditions, andfrom the ring-closed isomer B to the ring-open isomer A underelectrochemical conditions.

In another aspect, the compounds may be convertible from the ring-openisomer A to the ring-closed isomer B under a first photochemicalcondition, and from the ring-closed isomer B to the ring-open isomer Aunder a second photochemical condition. The first photochemicalcondition may include light within the UV range.

In another aspect, one or more of the compounds may be included in acomposition comprising one or more compounds, and one or moreformulation components.

As used herein, photochromic and photochemical both refer to conversionfrom one isoform to another when exposed to light. As used herein,electrochromic and electrochemical both refer to conversion from oneisoform to another when exposed to a voltage.

For visual clarity in some Formula and structures, abbreviatedsubstituent groups may be used in this text;

indicate the same substituents equivalent, with groups R_(6a), R_(6b),R_(6c) as described herein:

indicate the same substituents, with groups R_(7a), R_(7b) and R_(7c) asdescribed herein;

indicate the same substituents, with groups R_(8a), R_(8b), R_(8c)R_(8d), R_(8e), as described herein;

indicate the same substituents, with groups R_(9a), R_(9b), R_(9c),R_(9d) and R_(9e) as described herein;

indicate the same substituents, with groups R_(10a), R_(10b), R_(10c)and R_(10d) as described herein.

For compounds comprising two R₃ or two R₄ groups, both R₃ or both R₄groups may be the same or they may be different.

This summary does not necessarily describe all features. Other aspects,features and advantages will become apparent to those of ordinary skillin the art upon review of the following description of specificembodiments.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the absorbance (Y axis) of S001 at various wavelengths oflight (X axis, in nm) for two light sources—365 nm and solar simulator(SS) in the presence or absence of a UV blocking film. Solidline—absorbance plot of S001 in a faded state (“faded”-solid line); A-Dabsorbance plots with light source, +/−UV blocking film—A: Solarsimulator with UV blocking film; B: Solar simulator without UV blockingfilm; D: 365 nm light source without UV blocking film.

FIG. 2 shows a spectral profile for sunlight and interior halogen lightsources. Spectra are plotted on separate y-axes and do not reflectrelative intensities. The lighting conditions described in Table 9reflect different weighted sums of the two light sources shown resultingin the tabulated light intensities. X-axis wavelength of light in nm;left side Y-axis—sunlight intensity (solid line); right sideY-axis—interior light intensity (dotted line).

FIG. 3 shows the absorptivity of selected compounds at PSS underinterior lighting (A), combined interior and sunlight lighting (B), orsunlight (C). Y-axis shows the absorbance of ring-closed isomer at λmax. S096 (solid diamond), S094 (solid square), S079 (solid triangle),S044 (cross), S042 (star) and S035 (solid circle).

FIG. 4 shows a change in absorption of a sample of S094 exposed todifferent lighting conditions: solid line—sunlight (max PSS); dashedline—sunlight+interior lighting (photofaded from max dark tointermediate state); dotted line—interior lighting (photofaded from maxdark to lowest absorption state). X axis—elapsed time in seconds;Y-axis—absorbance.

FIG. 5 provides a bar graph illustrating the PSS of selected compoundsaccording to Formula IIA/IIB, in the ring-closed isoform (Formula IIB)when exposed to 365 nm light (open bar), or full spectrum light (QSUNsolar simulator) (solid bar). X-axis—compound reference numbers;Y-axis—absorbance.

FIG. 6 provides a bar graph illustrating the PSS of selected compoundsaccording to Formula IIIA/B, in the ring-closed isoform (Formula IIIB)when exposed to 365 nm light (open bar), or full spectrum light (solidbar). X-axis—compound reference numbers; Y-axis—absorbance.

FIG. 7 provides a bar graph illustrating the PSS of selected compoundsaccording to Formula IVA/B, in the ring-closed isoform (Formula IVB)when exposed to 365 nm light (open bar), or full spectrum light (solidbar). X-axis—compound reference numbers; Y-axis—absorbance.

FIG. 8 provides a bar graph illustrating the PSS of selected compoundsaccording to Formula VIIA/B, in the ring-closed isoform (Formula VIIB)when exposed to 365 nm light (open bar), or full spectrum light (solidbar). X-axis—compound reference numbers; Y-axis—absorbance.

DESCRIPTION OF THE INVENTION

There is provided, in part, novel and/or improved compounds having bothphotochromic and electrochromic functionality (“chromophores”, “hybridcompound”, “P/E compounds”). Without wishing to be bound by theory,diarylethenes, such as dithienylethenes, having ‘internal’ aryl groups(R₄ as illustrated in Formula IA and IB) exhibit both photochromic andelectrochromic functionality, and may be useful components of opticalfilters that vary in light transmissibility in response to stimuli. Somecombinations of substituent groups may provide for compounds withimproved or advantageous properties, including photostationary state,solubility, synthetic methods, sensitivity index, or the like.

There is further provided, in part, compounds that are reversiblyconvertible between a ring open isomer (Isomer A), and a ring-closedisomer (Isomer B). As used herein, a numeral or alpha-numeric reference(with suffix ‘A’) denotes the ring-open isomer of a compound, and aprimed numeral or alpha-numeric reference (with suffix ‘B’) or a primednumeral or alpha-numeric reference denotes the ring-closed isomer of thesame compound.

Compounds according to various embodiments may undergo catalyticelectrochemical oxidation with application of a voltage and methods ofswitching, or operating, a switching material from a dark to a fadedstate may employ application of a catalytic amount of a voltage. Acatalytic amount of a voltage may be positive or negative, and may befrom about 0.1 to about 5 volts, or any amount or range therebetween.

A “switching material” is one that has both electrochromic andphotochromic properties. A switching material may darken when exposed toultraviolet (UV) light from a light source, and may lighten (fade,electrofade) when exposed to a voltage. In some embodiments, theswitching material may fade upon exposure to selected wavelengths ofvisible (VIS) light (“photofade”), without sacrifice of the ability tobe electrofaded when restored to a darkened state.

As used herein, light transmittance may be described with reference to“Visible light transmittance” (VLT) or LT_(A) (luminous transmittance,illuminant A, 2% observer). Light transmittance may be expressed withreference to a change in light transmission and/or a particular type oflight or wavelength of light transmitted.

As used herein, “photostationary state” (PSS) refers an equilibriumstate of a compound or material where the rate of the ring closing(forward) reaction is equal to the rate of the ring-opening or fading(reverse) reaction, when irradiated with light in a given region of thespectrum; in other words, the ratio of ring-open isoform to ring-closedisoform is at an equilibrium. PSS may be expressed with reference to alight source, or with reference to a type of light—eg. QUV, Xenon-arclamp, Q-SUN, natural or filtered sunlight, UV, VIS, IR, NIR, fullspectrum, or the like, or with reference to a particular wavelength orrange of wavelengths, or in the presence or absence of a filter. Somering-open and ring-closed isomers may undergo isomerization from one tothe other in response to different wavelengths of light—if a wavelengthof light is used where only one of the isomers absorbs, irradiationresults in complete isomerization to the other form. 254 nm, 313 nm or365 nm light are commonly used in studies of UV-absorbing isomers, butthis may not be representative of the PSS under other light conditionsthat include the visible spectrum such as natural or simulated sunlight(“full spectrum” light) and/or with filters that block a portion of theUV component of the light. For example, in a ring-closed (dark) state,the magnitude of the maximum absorbance in the visible range may changewith the light source (FIG. 1)—the wavelength at this peak in thevisible range may be referred to as lambda max, or λmax. Line D showsthe absorption profile for a compound when exposed to a 365 nm lightsource. When full spectrum light from a solar simulator (Xenon arc lamp)is used as a light source (Line B), a balance is achieved between thering closed (dark) state induced by the UV component, and ring-open(faded) state induced by the visible component of the light. Inclusionof a UV blocking layer in the light path (Line A) may reduce the UVcomponent of the light, and the ring-opening reaction induced by thevisible light component becomes more prominent. Different compounds maydemonstrate different responsiveness to the composition of incidentlight. Depending on the use of a compound, one with greater or lesssensitivity to light composition may be useful. This equilibrium statemay be represented by an absorbance value at a particular wavelength(lambda max), and may include reference to a light source. Wheredesired, the ratio of ring-open and ring-closed isoforms at a PSS may bequantified by ¹H NMR spectroscopy.

As used herein, contrast ratio is a ratio of the light transmittance ofa material in the dark state and the light state. For example, amaterial may allow transmission of about 10% of the visible light (10%VLT) in a dark state, and about 60% of the visible light (60% VLT) in afaded state, providing a contrast ratio of 6:1. According to variousembodiments of the invention, a material may have a contrast ratio of atleast about 2 to about 20, or greater, or any amount or rangetherebetween, for example, about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19 or 20. In some embodiments, a compound with adarker PSS (greater absorbance at lambda max) may provide a greatercontrast ratio.

Photostability (resistance to light-induced degradation) may be measuredby the amount of time it takes for the compound, or a materialcomprising the compound to degrade to a certain point under lightexposure. The light exposure may be constant, or cyclic. The lighttransmittance or absorbance of the compound, or material comprising thecompound may be determined at both a light state and dark state prior totesting, to determine a contrast ratio. During testing, the contrastratio may be monitored (periodically or continually); the compound ormaterial may be determined to have failed when the contrast ratio fallsoutside, or below, a selected range, or when the contrast ratiodecreases to a percentage of the original contrast ratio. Photostabilityalso, may be expressed with reference to a light source or withreference to a type of light.

As used herein “switching voltage” (“switching potential”, “potential”)refers to the electric potential required for a compound, or material,to achieve a faded state. Switching voltage may further refer to therelationship between voltage and time to switch. To assess the switchingvoltage of a material, the material may be first darkened by exposure toa light source, followed by passing an electric current through thematerial at a defined voltage or voltage range, and assessing the timeuntil a clear state, or a desired increase in light transmissibility isachieved. Switching voltage may be expressed as a voltage or range ofvoltage (e.g. about 2.5 volts, about 2.2 volts, or below about 2 volts,or the like). In some embodiments of the invention, the compound ormaterial has a switching potential of about 0.5 volts to about 5 volts,or from about 1 volt to about 2.5 volts, or any amount or rangetherebetween.

As used herein “switching time” refers to the time necessary for amaterial to transition from a dark state to a clear state, or from aclear state to a dark state, or to alter light transmittance by adefined amount.

“About” as used herein when referring to a measurable value such as anamount, a temporal duration, or the like, is meant to encompassvariations of ±20% or ±10%, or ±5%, or ±1%, or ±0.1% or any amounttherebetween from the specified value, as appropriate to perform thedisclosed methods.

As used herein, “halogen” refers to F, Cl, Br or I. The term “halo” isgeneric, and refers to any halogen moiety, for example fluoro-chloro-,bromo- or iodo-, or the like.

As used herein, “metal” as used herein refers to a transition metal, oran alkali metal such as Li, Na, K, or the like; or a metalloid such as Bor Si, or the like.

As used herein, “alkyl” refers to any linear or branched, non-aromaticmonocyclic or polycyclic, substituted or unsubstituted alkyl group of 1to 50 carbons, for example 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 25, 30, 35, 40, or 45, or any amounttherebetween. Examples of alkyl groups include methyl, ethyl, propyl,isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, 1-pentyl,iso-pentyl, neo-pentyl, hexyl, cyclopropane, cyclobutane, cyclopentane,cyclohexane or the like. The alkyl group may have one or more saturatedor unsaturated bonds. The alkyl group may contain only carbon andhydrogen atoms, or may further incorporate one or more heteroatoms suchas Si, N, O or S as part of the alkyl group (a heteroalkyl group).Examples of cyclic heteroalkyl groups include aziridine, oxirane,thiirane, oxaziridine, dioxirane, azetidine, oxetane, thietane,diazetidine, dioxetane, dithietane, azirine, oxirene, thiirene, azete,oxete, thiete, dioxete, dithiete, pyrrolidine, oxolane, thiolane,borolane, silolane, dithiolane, dioxolane, oxazolidine, piperidine,oxane, thiane, piperazine, morpholine or the like. An alkyl group withan Si heteroatom may be described as a ‘silyl’ or ‘silane’ group.

As used herein, “alkoxy” refers to any —O—R group, where R (and R′ foran ether, below) may independently be H, alkyl, siloxy or aryl. Examplesof alkoxy groups include those with from 1 to 50 carbon or silicon atomsin a linear or branched chain, for example methoxy or ethoxy, or longeralkyl groups. Other alkoxy groups include ethers (—R—O—R′—), alcohol(—OH) or alkoxide (—R—O-metal) or the like. An alkyl group comprising analkoxy substituent group may be referred to as an ‘alkylalkoxy’ group.An alkyl group comprising an Si heteroatom, and an alkoxy, or a siloxygroup may be referred to as an alkylsiloxy, or silylsiloxy group.

As used herein, “carbonyl” refers to any group comprising RRC═O, where Rmay be any group. Examples of carbonyl groups include aldehyde (—COH),ketone (COR′), ester (COOR′), acyl (RR′C═O), carboxyl, thioester(COSR′), primary amide (CONH₂), secondary amide (CONHR′), tertiary amide(CONR′R″) or the like.

As used herein, “siloxane” refers to an (R)₂—Si—O—, where R mayindependently be H, alkyl, aryl, thioether or alkoxy. A siloxane may bebranched or linear, substituted or unsubstituted, or comprisealternating Si and O atoms.

As used herein, “thioether” refers to an —S—R group where R mayindependently be H, alkyl, aryl, alkoxy or the like.

R′, R″, R′″ may be alkyl chains that contain between 1 and 50non-hydrogen atoms such as C, N, O, S, Si, B or P that may be branchedor unbranched, that may be acyclic or cyclic, and that may contain anypermutation of heteroatomic substituents such as N, O, S, Si, B orhalogen.

As used herein, “aryl” refers to a group or substituent derived from anaromatic ring compound where one or more hydrogen atoms are removed fromthe ring. An aryl group may alternately be referred to as an aromaticgroup. An aryl group may comprise a single atom species in the ring(e.g. all ring atoms may be carbon, such as in a phenyl ring—a‘carbocycle’) or may comprise one or more heteroatoms in the ring—a“heteroaryl”. An aryl group may be polycyclic. The carbocyclic,heterocyclic or polycyclic aryl group may comprise one or moresubstitutent groups (a substituted aryl) or be unsubstituted (anunsubstituted aryl). A carbocyclic aryl group may be substituted orunsubstituted phenyl or the like. A carbocyclic aryl group may bepolycyclic.

A heterocyclic aryl group may be substituted or unsubstituted pyrrole,furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole,isothiazole, triazole, furazan, oxadiazole, thiadiazole, dithiazole,tetrazole, pyridine, pyran, thiopyran, diazine, oxazine, thiazine,dioxine, dithiine, triazine, tetrazine, or the like.

A polycyclic aryl group may be substituted or unsubstituted indole,isoindole, quinolone, isoquinoline, benzofuran, benzothiophene,acridine, dibenzothiophene, carbazole, dibenzofuran or the like.

As used herein, alkyl, heteroalkyl, alkoxy, alkylalkoxy or aryl groupsmay further comprise 1, 2, 3, 4, 5 or more substituent groups.Substituent groups may be independently selected from the groupscomprising:

(i) hydrogen or halogen;

(ii) alkyl or alkoxy;

(iii) a derivative of group (ii) above in which one or more of thecarbon atoms have been replaced with a heteroatom such as nitrogen,oxygen, sulfur, boron, silicon or phosphorous;

(iv) a derivative of groups (ii), (iii), or (ii) and (iii) above inwhich one or more of the hydrogen atoms have been replaced with aheteroatom such as nitrogen, oxygen, sulfur, fluorine, chlorine orbromine;

(v) a monocyclic or bicyclic cycloalkyl group containing from one tofifteen carbon atoms, or the like;

(vi) a derivative of group (v) above in which one or more of the carbonatoms have been replaced with a heteroatom such as nitrogen, oxygen,sulfur, boron, silicon or phosphorous;

(vi) a derivative of groups (v), (vi), or (v) and (vi) above in whichone or more of the hydrogen atoms have been replaced with a heteroatomsuch as nitrogen, oxygen, sulfur, fluorine, chlorine or bromine;

(vii) an aryl group;

(viii) a derivative of group (vii) above in which one or more of thehydrogen atoms have been replaced with a heteroatom such as nitrogen,oxygen, sulfur, fluorine, chlorine or bromine;

(ix) a carbonyl group;

(x) a nitrogen-based group such as cyano (—CN), primary amine (NH₂),secondary amine (NHR′), tertiary amine (NR′R″), secondary amide(NHCOR′), tertiary amide (NR′COR″), secondary carbamate (NHCOOR′),tertiary carbamate (NR′COOR″), urea or N-substituted urea (NR′CONR″R′″),secondary sulfonamide (NHSO₂R′), tertiary sulfonamide (NR′SO₂R″),wherein groups R′, R″, R′″, are defined supra;

(xi) an oxygen-based group e.g alcohol —OH, ether (OR′), primarycarbamate (OCONH₂) secondary carbamate (OCONHR′), tertiary carbamate(OCONR′R″), wherein groups R′, R″, etc., are defined supra.

(xii) a sulfur-based group such as —SH, thioether (SR′), sulfoxide(SOR′), sulfone (SO₂R′), primary sulfonamide (SO₂NH₂), secondarysulfonamide (SO₂NHR′), tertiary sulfonamide (SO₂NR′R″), wherein groupsR′, R″, R′″ are defined supra.

In some aspects of the invention, R_(6a), R_(6b), R_(6c), R_(7a),R_(7b), R_(7c) R_(8a), R_(8b), R_(8c), R_(8d), R_(8e), R_(9a), R_(9b),R_(9c), R_(9d), R_(9e), R_(10a), R_(10b), R_(10c), R_(10d) mayindependently comprise an electron-withdrawing group (EWG),electron-donating group (EDG) or bulky group. It should be understoodthat the term “electron-accepting group” can be used synonymously hereinwith “electron acceptor” and “electron-withdrawing group”. Inparticular, an “electron-withdrawing group” (“EWG”) or an“electron-accepting group” or an “electron-acceptor” refers to afunctional group that draws electrons to itself more than a hydrogenatom would if it occupied the same position in a molecule. Examples ofEWG include halo, electron-poor heteroaryl groups, electron-poorsubstituted aryl groups, —NO₂, —⁺NR₃, —⁺NH₃, —SO₃H, —CN, CF₃, aldehyde,ester, carboxylic acid, carbonyl, carbonyl chloride, amide or the like.It should further be understood that the term “electron-donating group”can be used synonymously herein with “electron donor”. In particular, an“electron-donating group” or an “electron-donor” refers to a functionalgroup that donates electrons to a neighboring atom more than a hydrogenatom would if it occupied the same position in a molecule. Examples ofEDG include —OH, OR, NH₂, NHR, NR₂, electron-rich heteroaryl groups,electron-rich substituted aryl groups, —O—, amine, alcohol, ether,carbamate, or the like.

A substituent group may comprise a siloxy or silyl component—for examplesilane, siloxy, alkylsiloxy, silanesiloxy, alkoxysilane, Formula XI,Formula XII, or the like—the substituent group may comprise:

wherein n and m are independently any integer from 0 to 20, or any rangetherebetween, or 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19 or 20.

A “bulky” group may be an alkyl, aryl, alkoxy, silane, siloxy,alkylsiloxy, silanesiloxy, alkoxysilane, or a substituted alkyl, aryl,alkoxy, silane, siloxy, alkylsiloxy, silanesiloxy, alkoxysilane, thebulky substituent group comprising at least two atoms selected from thegroup comprising C, N, O, Si or S. In some embodiments, a bulkysubstituent group is a substituted or unsubstituted ethyl, propyl,butyl, tert-butyl or pentyl group, or a substituted or unsubstitutedalkoxy group. In some embodiments, a bulky substituent group is asubstituted or unsubstituted formula XI or formula XII. In someembodiments, a bulky substituent group is an alkyl-substitutedthiophene, or an alkyl-substituted phenyl, or an alkyl substitutedbenzothiophene or an alkyl substituted benzofuran.

Inclusion of a bulky substituent group may increase the, photostationarystate, solubility, photostability or durability of a compound. As anillustrative example, and without wishing to be bound by theory, somepositions of an internal or external thiophenyl ring may polymerize whensubjected to oxidation conditions by application of a voltage. Inclusionof a bulky group at R_(6a) or R_(7a) (5-position), or R_(6b) or R_(7b)(4-position) of a thiophenyl ring may improve the durability of thecompound when subjected to multiple cycles of electrooxidation. In someembodiments, a small (e.g. 1 or 2 carbon containing moieties such asmethyl or ethyl) group in both 4 and 5 positions, or a larger bulkygroup (e.g. 3, 4, 5 or 6 carbon-containing moieties such as propyl,butyl (primary, secondary or tertiary), pentyl or hexyl in the 5position may provide improved durability of the compound.

Compounds according to various embodiments of the invention may includeone or more of the following:

Each R₁ and R₂ may be independently selected from a group comprising Hor F.

R₃ and R₄ may each be independently selected from a group comprising oneor more than one of thiophenyl, substituted thiophenyl, benzyl,substituted benzyl,

In some embodiments, the group from which R₃ may be selected may furthercomprise one or more of H, Cl, Br, F, CF₃, methyl, ethyl, propyl, butyl,tert-butyl, —CH₂—CH₂—, —CH═CH—, —OCH₃, CO₂H, COCH₃, CO₂Y, C(CH₃)₂OH,Si(CH₂)₃OCH₃, Si(CH₃)₃, Si((CH₂)₃)CH₃)₃CH₂CH₂OCH₃, CH₂CH₂OH,

Each R₅ may be independently selected from a group comprising: H,methyl, ethyl, propyl, butyl, tert-butyl, thiophenyl, substitutedthiophenyl, benzyl, substituted benzyl, —CH═CH—, —CH═CH—, —OCH₃, CO₂H.

R₃ and R₅ may each be —CH═CH— and fused to form a ring, or R₃ and R₅ mayeach be —CH₂—CH₂— and fused to form a ring;

Substituent groups of a substituted thiophene or substituted benzylgroup may include —CN, methyl, ethyl, propyl, butyl, tert-butyl;

R_(6a) and R_(6b), or R_(6b) and R_(6c), or R_(7a) and R_(7b), or R_(7b)and R_(7c) may each be a) —CH═CH— and fused to form a ring; or b)—CH₂—CH₂— and fused to form a ring; or c) —O—CH₂— and fused to form aring;

One or more than one of: R_(6a), R_(6b), R_(6c); and/or R_(7a), R_(7b),R_(7c); and/or R_(8a), R_(8b), R_(8c), R_(8d), R_(8e); and/or R_(9a),R_(9b), R_(9c), R_(9d), R_(9e); and/or R_(10a), R_(10b), R_(10c),R_(10d) may each independently be selected from a group comprising oneor more of: H, Cl, Br, F, —CF₃, —CN, —NO₂, methyl, ethyl, propyl,iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated orunsaturated alkyl that is linear or branched with 5-12 carbons,—Si(R₁₁)₃, thiophene, substituted thiophene, benzyl, substituted benzyl,—CH₂—CH₂—, —CH═CH—, —CH═CH₂, —OCH₃, —COH, —OH, —CO₂H, —COCH₃, —CO₂Y,—C(CH₃)₂OH, —Si(CH₃)₃, —CH₂CH₂OCH₃, —CH₂CH₂OH, —N(CH₃)₂, —CO₂CH₃,—OCH₂OCH₃, —SO₂CH₃, —OCH₂C(CH₃)₃, —OCH₂CH(CH₃)₂, —OC(CH₃)₃, —OCH═CH₂,—O(CH₂)₄CN, —O(CH₂)₄OH, —O(CH₂)₃OH, —C(CH₃)₂OH, —OCH₂)₂OCH₃,

In some embodiments, each R₁₁ of —Si(R₁₁)₃ may be independently selectedfrom the group comprising R or —O—R, and wherein R is linear orbranched, non-aromatic monocyclic or polycyclic, substituted orunsubstituted alkyl group of 1 to 20 carbons. In some embodiments, eachR may be a heteroalkyl group comprising one or more of O, S, N or Si, oreach R may be a saturated or unsaturated alkyl that is linear orbranched with 1-12 carbons, or each R may be a substituted orunsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl,iso-butyl, tert-butyl, pentyl or hexyl.

Exemplary compounds according to Formulae IA and IB include: S039, S053,S073, U130, U136, U142.

Exemplary compounds according to Formulae IIA and IIB (compoundsaccording to Formula IA/IB where R₃ is

and R₄ is

include one or more of: S001, S003, S007, S011, S012, S013, S019, S020,S024, S026, S027, S034, S036, S037, S038, S040, S047, S048, S106, S119,S124, S128, S135, S138, S143, S148, S149, S154, S158, S170, U008, U009,U010, U018, U021, U022, U023, U025, U028, U029, U030, U041, U100, U102,U117, U120, U125, U126, U127, U129, U131, U132, U133, U134, U156, U159,U160, U165, S170.

Exemplary compounds according to Formulae IIIA and IIIB (compoundsaccording to Formula IA/IB where R₃ is

and R₄ is

include one or more of: S002, S006, S016, S017, S042, S043, S044, S050,S054, S056, S057, S059, S060, S063, S064, S065, S066, S067, S068, S074,S084, S085, S086, S087, S088, S089, S090, S091, S092, S094, S095, S096,S097, S103, S116, U031, U051, U058, U061, U062, U069, U070, U071, U072,U076, U077, U078, U080, U081, U093, U099, U101.

Exemplary compounds according to Formulae IVA and IVB (compoundsaccording to Formula IA/IB where R₃ is

and R₄ is

include one or more of: S052, S098, S104, S105, S108, S109, S110, S111,S112, S113, S115, S118, S139, S141, U107, U114, U122, U123.

Exemplary compounds according to Formulae VA and VB (compounds accordingto Formula IA/IB where R₃ is

and R₄ is

include: S049

Exemplary compounds according to Formulae VIA and VIB (compoundsaccording to Formula IA/IB where a first R3 is

and a second R₃ is

and a first R4 is

and a second R4 is

include one or more of: S004, S005.

Exemplary compounds according to Formula VIIA and VIIB include one ormore of: S014, S015, S079, S083, S137, S140, S144, S157, U082, U121,U142, S144, U145, U146, U147, U150, S151, S152, U153, S155, U157, S161,S162, S163, S164.

Exemplary compounds according to Formulae VIIIA and VIIIB (compoundsaccording to Formula VIIA/B where R4 is

include one or more of S014, S015, S079, S083, S140, S157, U082, U121,S144, U142, U145, U146, U147, U150, S151, U153, S155, U157, S161, S162,S163, S164, S191 and S193.

Exemplary compounds according to Formulae IXA and IXB (compoundsaccording to Formula VIIA/B where R4 is

include one or more of S137, S144, S152.

Exemplary compounds according to Formulae XA and XB include one or moreof S191 and S193.

Other exemplary compounds according to various embodiments of theinvention include one or more of: S032, S035, S055, U045.

In some embodiments, compounds with an increased absorbance at aphotostationary state (PSS) or a suitable, or increased contrast ratio,or an increased solubility may be an improvement. A compound with agreater absorbance in the visible range may be used in lesser quantitiesin a formulation or material to achieve a desired contrast ratio,whereas a compound with a lower absorbance at a PSS may need a higherconcentration to achieve a desired contrast ratio. Absorbance at a PSSfor selected compounds was measured at 2.0×10⁻⁵ M in triglyme in theabsence (full) or presence (+UV) of a UV blocking film with a UV cutoffwavelength of 370 nm (10% transmission at 370 nm), using simulatedsunlight (QSUN solar simulator) as a light source, or a 365 nm lightsource; these PSS are reported in Tables 1.5. All of the compoundsdemonstrated electroswitching. “Switch” refers to the ability (yes orno) of the compound to be reversibly converted under photochromic andelectrochromic conditions between a ring-open isomer and ring-closedisomer.

In addition to an electrochromic ring-opening isomerization, compoundsaccording to various embodiments of the invention also exhibit aphotochromic ring-opening isomerization when exposed to visible light. Asensitivity index (SI) is a ratio of the PSS under 365 nm light to thePSS under full spectrum light (without UV blocking film). SI is anindicator of the sensitivity of the compound to the composition of theincident light (a change in the ratio of UV and visiblecomponents)—photochemical ring-opening is induced by a portion of thevisible light spectrum. An SI of about 1 indicates that the rate ofphotoconversion to the ring-closed state is about equal with both lightsources, whereas as the SI increases it is indicative of a greatersensitivity to the composition of the light source.

Applications that may benefit from a higher rate of photoconversion to aring-closed state may benefit from a compound having a higher PSS, whileapplications that may benefit from a low rate of photoconversion to aring-closed state may benefit from a lower PSS. Applications that maybenefit from a compound that is less responsive to the light compositionmay benefit from a compound having an SI closer to 1, whereasapplications that may benefit from a compound that exhibits a highersensitivity to the composition of light may benefit from a compound witha higher SI.

TABLE 1 Absorbance at PSS for selected chromophores according toFormulae IIA and IIB. FIG. 5 provides a bar graph illustrating the PSSof Formula II compounds in the ring-closed isoform (Formula IIB) whenexposed to 365 nm light (365 nm), or simulated sunlight. sensitivitycompound λ max full +UV 365 nm Switch index S024 650 0.02 0.018 0.102 Y5.10 S036 665 0.024 0.016 0.174 Y 7.25 S020 665 0.115 0.085 0.244 Y 2.12S148 650 0.15 0.092 0.244 Y 1.63 S027 645 0.156 0.116 0.281 Y 1.80 S001640 0.182 0.113 0.309 Y 1.70 S011 655 0.201 0.142 0.363 Y 1.81 S007 6500.212 0.154 0.353 Y 1.67 S149 647 0.241 0.169 0.339 Y 1.41 S124 6490.249 0.225 0.344 Y 1.38 S026 645 0.251 0.196 0.383 Y 1.53 S128 6480.264 0.224 0.403 Y 1.53 S003 650 0.2655 0.2055 0.372 Y 1.40 S034 6900.271 0.246 0.468 Y 1.73 S170 645 0.287 0.182 0.401 Y 1.40 S138 6500.306 0.262 0.337 Y 1.10 S135 648 0.318 0.224 0.387 Y 1.22 S158 6500.342 0.291 0.394 Y 1.15 S119 643 0.343 0.295 0.405 Y 1.18 S037 6800.375 0.355 0.442 Y 1.18 S038 690 0.456 0.431 0.642 Y 1.41

TABLE 2 Absorbance at PSS for selected chromophores according toFormulae IIIA and IIIB. FIG. 6 provides a bar graph illustrating the PSSof Formula III compounds in the ring-closed isoform (Formula IIIB) whenexposed to 365 nm light (365 nm), or simulated sunlight. sensitivitycompound λ max full +UV 365 nm Switch index S017 605 0.009 0.0025 0.049Y 5.44 S002 612 0.0325 0.0095 0.116 Y 3.57 S006 610 0.038 0.013 0.141 Y3.71 S096 609 0.045 0.014 0.183 Y 4.07 S044 605 0.062 0.027 0.222 Y 3.58S067 615 0.068 0.03 0.182 Y 2.68 S074 620 0.069 0.024 0.189 Y 2.74 S056610 0.071 0.026 0.194 Y 2.73 S097 611 0.073 0.029 0.206 Y 2.82 S075 6700.079 0.031 0.302 Y 3.82 S057 610 0.079 0.033 0.204 Y 2.58 S084 625 0.090.051 0.23 Y 2.56 S042 612 0.097 0.04 0.233 Y 2.40 S066 615 0.099 0.0490.226 Y 2.28 S054 630 0.106 0.056 0.268 Y 2.53 S060 615 0.107 0.038 0.22Y 2.06 S090 624 0.107 0.058 0.183 Y 1.71 S087 628 0.109 0.055 0.209 Y1.92 S068 615 0.111 0.051 0.239 Y 2.15 S086 610 0.115 0.071 0.231 Y 2.01S089 656 0.137 0.126 0.564 Y 4.12 S065 625 0.138 0.054 0.281 Y 2.04 S095625 0.16 0.086 0.279 Y 1.74 S085 640 0.161 0.08 0.187 Y 1.16 S092 6270.162 0.093 0.307 Y 1.90 S091 629 0.164 0.095 0.287 Y 1.75 S094 6250.179 0.103 0.311 Y 1.74 S088 656 0.202 0.132 0.457 Y 2.26

TABLE 3 Absorbance at PSS for selected chromophores according to FormulaIVA and IVB. FIG. 7 provides a bar graph illustrating the PSS of FormulaIV compounds in the ring-closed isoform (Formula IVB) when exposed to365 nm light (365 nm), or simulated sunlight. sensitivity compound λ maxfull +UV 365 nm Switch index S049 625 0.087 0.044 0.217 Y 2.49 S105 6470.197 0.134 0.272 Y 1.38 S052 630 0.206 0.116 0.318 Y 1.54 S118 6480.223 0.124 0.34 Y 1.52 S098 645 0.273 0.182 0.377 Y 1.38 S112 663 0.2780.246 0.318 Y 1.14 S141 643 0.282 0.183 0.377 Y 1.34 S111 646 0.2920.192 0.322 Y 1.10 S108 645 0.292 0.215 0.374 Y 1.28 S109 645 0.2960.217 0.367 Y 1.24 S104 645 0.299 0.203 0.383 Y 1.28 S139 644 0.3220.216 0.403 Y 1.25 S110 653 0.346 0.221 0.414 Y 1.20 S113 643 0.4170.293 0.514 Y 1.23 S115 644 0.567 0.401 0.71 Y 1.25

TABLE 4 Absorbance at PSS for selected chromophores according to FormulaVIIA and VIIB. FIG. 8 provides a bar graph illustrating the PSS ofFormula VII compounds in the ring-closed isoform (Formula VIIB) whenexposed to 365 nm light (365 nm), or simulated sunlight. sensitivitycompound λ max full +UV 365 nm Switch index S014 525 0.004 0.006 0.011 Y2.75 S073 550 0.0105 0.006 0.06 Y 5.71 S079 490 0.023 0.008 0.17 Y 7.39S083 550 0.023 0.008 0.167 Y 7.26 S137 497 0.033 0.016 0.15 Y 4.55 S039570 0.048 0.028 0.372 Y 7.75 S140 516 0.065 0.032 0.276 Y 4.25 S152 5220.069 0.06 0.263 Y 3.81 S155 516 0.081 0.045 0.329 Y 4.06 S144 513 0.0820.04 0.318 Y 3.88 S151 514 0.106 0.056 0.403 Y 3.80 S162 520 0.119 0.060.398 Y 3.34 S161 511 0.122 0.06 0.455 Y 3.73 S164 554 0.235 0.134 0.546Y 2.32 S163 588 0.252 0.116 0.533 Y 2.12

TABLE 5 Absorbance at PSS for selected chromophores. sensitivitycompound λ max full +UV 365 nm Switch index S032 600 0.032 0.008 0.594 Y18.56 S055 640 0.042 0.008 0.191 Y 4.55 S035 540 0.05 0.016 0.416 Y 8.32S004 630 0.0325 0.02 0.139 Y 4.28 S005 618 0.072 0.028 0.195 Y 2.71

Absorbance at a PSS, or the wavelength of maximum absorbance may varywith the substituent groups. Table 6 sets out some observations on theeffect of various components, structures and substituent groups on PSS.

TABLE 6 PSS comparison of selected compounds. Relative impact ofsubstituent groups on photostationary state is indicated with “✓”(increase) and “ 

 ” (decrease); — No data; N/A: Not applicable. Formula Formula IIFormula III IV Head Perfluorocyclopentene ✓ ✓ — Thiazole derivative

✓ 

— Core ring Thiophene ✓✓ ✓✓ ✓✓ Thiazole — ✓ — Benzothiophene — —

Benzofuran — —

Steric groups All ✓✓ ✓✓ ✓✓ External ✓✓ ✓✓ ✓✓ Internal ✓ ✓ ✓ EDG All

✓✓ — External — ✓✓ — Internal — ✓ 

✓✓ EWG All ✓✓

— External ✓✓

— Internal ✓✓

— Peripheral thiophene R3 ✓✓✓ N/A ✓✓✓ rings position R4 ✓ N/A ✓ positionPhenyl R3 N/A

positsion R4 N/A

✓ 

position Extended π-conjugation ✓✓✓ ✓ 

— 4-Position core thiophene —

— 4-Position peripheral thiophene

— — Position of EDG para — ✓✓ — meta —

—

The effect of different substitutent groups on PSS may be considered.Compare compounds of the same, or different formula; for example:

-   -   “head” structures of S032, S035, S055 and/or S075;    -   core structure of S014, S032, S035, S079 and/or S083;    -   peripheral rings—groups in the R3 and/or R4 position of 8001,        S002, S003, S038, S049, S052, S088, S104, S108, S109, S138        and/or S158;    -   substituent groups of S001, S007, S003, S042, S057, S110, and/or        S068;    -   electron withdrawing groups (EWG) and electron donating groups        (EDG) of S002, S003, S020, S026, S034, S036, S037, S054, S074,        S085, S086, S087, S096, S097, S098, S12, S118, and/or S119;    -   extended conjugation of S034, S037, S038, S088, S089 and/or        S110;    -   position and species of substituent groups of S054, S091, S092,        S094 and/or S095;    -   substituent group size or length and composition of S098, S104,        S105, S108, S109, S111, S113, S115, S138, S158, S170.

Other compounds described herein may be included in such comparisons ofcompounds and be instructive in selecting a compound according tovarious embodiments of the invention. Inclusion of some substituentgroups may increase or decrease PSS or solubility or a combinationthereof. For example, inclusion of “bulky”, EWG or EDG substituentgroups may improve absorbance at a PSS for some compounds in a family.

According to various embodiments of the invention, a compound accordingto Formula IIA/IIB, or IIIA/IIIB, or IVA/IVB, or VA/VB, or VIA/VIB, orVIIA/VIIB, or VIIIA/VIIIB, or XIA/XIB, or XA/XB may have an SI of about1 to about 20, or any amount or range therebetween, for example, about2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or anyamount or range therebetween; or about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0,3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8 or 3.9, or any amount or rangetherebetween.

According to various embodiments of the invention, a compound accordingto Formula IIA/IIB, or IIIA/IIIB, or IVA/IVb, or VA/VB, or VIA/VIB, orVIIA/VIIB, or VIIIA/VIIIB, or XIA/XIB, or XA/XB may have a PSS under 365nm or full spectrum light (simulated sunlight) of about 0.05 to about 2or any amount or range therebetween for example about 0.05, 0.1, 0.2,0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,1.7, 1.8, 1.9 or 2.0, or any amount or range therebetween. In someembodiments the compound may have a PSS under 365 nm or full spectrumlight (simulated sunlight) of at least 0.05 to about 2 or any amount orrange therebetween for example at least 0.05, 0.1, 0.2, 0.3, 0.4, 0.5,0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or2.0, or any amount or range therebetween.

A compound with greater solubility allows for a formulation or materialwith a greater concentration of coloured molecule to be incorporatedinto a composition. This may allow for increasing the contrast ratio fora compound with a lesser absorbance at PSS. Inclusion of a solubilizinggroup in a compound according to various embodiments of the inventionmay increase solubility. Examples of solubilizing groups may includealkoxy or siloxy groups.

TABLE 7 Solubility for selected chromophores. Solubility = % wt solublein indicated solvent. compound Solvent Solubility S001 triglyme 5-6 S002Triglyme   1-1.5 S003 Triglyme <3 S006 Triglyme 3 S011 Triglyme 3 S017Triglyme 1 S020 Triglyme 3 S032 Triglyme 1 S039 Triglyme 2 S042 Triglyme0.5 S044 Triglyme 1 S049 Triglyme 2 S052 Triglyme 1 S054 Triglyme 5-6S057 Triglyme 1.5 S060 Triglyme 1 S066 Triglyme 2.5 S068 Triglyme >20S075 Triglyme 1 S079 Triglyme  8-11 S096 Triglyme 15 S098 Triglyme 1.5S108 Triglyme >25 S109 Triglyme >25 S128 Triglyme >25 S138 Triglyme >20S158 Triglyme >20

Compounds of the invention may be in a monomeric or polymeric form. Insome embodiments, the polymeric form may be a homopolymer orheteropolymer; the polymeric form may be produced by a ring-openingmethathesis polymerization (ROMP). Examples of ROMP conditions forpolymer production with a photochromic moiety in a side chain or a mainchain of the polymer are described for selected1,2-bis(3-thienyl)cyclopentene molecules in PCT Publications WO 02/06361and WO2004/015024, respectively.

In some embodiments, where compounds according to any of Formulae IA andIB, IIA and IIB, IIIA and IIIB, IVA and IVB, VA and VB, VIA and VIB,VIIA and VIIB, VIIIA and VIIIB, XIA and XIB or XA and XB, where both R₂are —CH═CH— and joined to form a cyclic structure, a homopolymer orheteropolymer may be produced using the ROMP method and conditionsdescribed in PCT Publication WO2004/015024.

In some embodiments, for compounds according to Formulae IA and IB whereR₃ is CO₂Y and R₄ is aryl, a homopolymer or heteropolymer havingphotochromic and electrochromic properties maybe produced using the ROMPmethods and conditions described in PCT Publication WO02/06361. In someembodiments, R₁ and R₂ may be F.

In some embodiments where compounds according to any of Formulae IIA andIIB, IVA and IVB, VIA and VIB, one of R_(6a-c) is CO₂Y, and ahomopolymer or heteropolymer having photochromic and electrochromicproperties may be produced using the ROMP methods and conditionsdescribed in PCT Publication WO02/06361. In some embodiments, R₁ and R₂may be F. S048 is an example of a compound of the invention that may beincorporated into a polymeric composition according to some embodimentsof the invention.

In some embodiments where compounds according to any of Formulae IIIAand IIIB, VA and VB, VIA and VIB, one of R_(8a-c) is CO₂Y, and ahomopolymer or heteropolymer having photochromic and electrochromicproperties may be produced using the ROMP methods and conditionsdescribed in PCT Publication WO02/06361. In some embodiments, R₁ and R₂may be F.

In some embodiments where compounds according to any of Formulae VIIAand VIIB, VIIIA and VIIIB, XIA and XIB or XA and XB, one of R_(10a-d)and/or one of R_(6a-c) is CO₂Y, and a homopolymer or heteropolymerhaving photochromic and electrochromic properties maybe produced usingthe ROMP methods and conditions described in PCT Publication WO02/06361.In some embodiments, R₁ and R₂ may be F.

Formulation and Switching Materials

The invention also relates to compositions comprising one or morecompounds, and one or more formulation components. The invention alsorelates to compositions comprising one or more formulation components,in the absence of a compound. Examples of formulation components includea solvent and optionally a supporting electrolyte and a gelling agent. Aformulation may further comprise one or more of a polymer, a polymer, amonomer, an initiator, a catalyst, an electrolyte, a charge compensator,anti-oxidant, a rheology modifier, a colourant (dye, non-switchingchromophore), a UV blocking agent, or the like. Those skilled in the artwill recognize that a formulation component may perform one or more thanone function. For example, compounds comprising polymeric compositions,and the polymeric composition included in a material may provide asingle formulation component that provides both a switching function, aswell as a structural or rheological function.

A switching material may have a VLT or LT_(A) of at least about 50%, atleast about 60%, at least about 70%, at least about 80% or at leastabout 90% when in a light state, or any amount or range therebetween,according to various aspects of the invention. Alternately, a switchingmaterial may have a VLT or LT_(A) of less than about 50%, or less thanabout 40% or less than about 30% or less than about 20% or less thanabout 10% when in a dark state, or any amount or range therebetween,according to various aspects of the invention.

One or more compounds according to various embodiments of the inventionmay be present in a switching material in an amount (% weight) of about0.05% to about 30%, or any amount or range therebetween, for exampleabout 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, 21, 22, 23, 24, 25, 26, 27, 28 or 29%.

Suitable solvents include those with one or more of the followingcharacteristics: boiling point of about 150° C. or greater, vapourpressure of about 0.001 mmHg or less at 20° C., Yellowness Index (YI) ofabout 6 or less; a flash point of about 80° C. or greater, a meltingpoint of about 40° C. or less. In some embodiments, the solvent does nothave HCN or HCl degradation products, or does not have —NH, urea orketone functional groups. Examples of solvents include, but are notlimited to triglyme, tetraglyme, propylene carbonate, ethylenecarbonate, water, butyrolactone, cyclopentanone or a combinationthereof.

Further examples of solvents include ethylene glycol phenyl ether;diethylene glycol monobutyl ether; diethyl succinate; dimethylglutarate;N-methylpyrrolidone (NMP)ethyl myristate; mineral seal oil; diethyleneglycol n-butyl ether acetate; Eastman C11 ketone; diisobutyl adipate;dihexyl azelate; diethyl maleate; diisooctyl azelate; triethylene glycolmonobutyl ether (butoxytriglycol); diisooctyl dodecanedioate;2-(2-ethylhexyloxy)ethanol; glyceryl triacetate; tetramethylenesulfoxide; dibutyl adipate; 3-dodecylheptamethyltrisiloxane; diethylsebacate; dibutyl itaconate; 1,4-Butanediol; butyl sulfoxide; diethyleneglycol; octyl octanoate; hexyl octanoate; diisodecyl adipate; diethyleneglycol monoethyl ether acetate; 1,3/1,4-cyclohexanedimethanol (CHDM);1-Decanol; 2-methylglutaronitrile; methyl palmitate; tri(propyleneglycol)butyl ether, mixture of isomers (Dowanol™ TPnB); 1-Dodecanol;tetradecane; diethylene glycol hexyl ether; dioctyl ether; methylstearate; hexyl hexanoate; butyl diglyme; triisopentylamine;Bis(2-ethylhexyl) sebacate; 1,5-dicyanopentane; diisobutyl fumarate;2,2,4-trimethyl-1,3-pentanediol dibenzoate; poly(ethyleneglycol)monolaurate; isooctyl tallate; poly(ethylene glycol)monooleate;hexaethyldisiloxane; poly(ethylene glycol)dioleate; triethylene glycoldi-2-ethyl butyrate (TEG DEB); tributyrin (butanoic acid),1,2,3-propanetriyl ester; tetramethylene sulfone (sulfolane);polyethylene glycol dimethyl ether m.w.˜250 (PEG-DME 250); ethylenecarbonate (EC); bis(2-ethylhexyl) adipate; tetraethylene glycol;hexadecamethylheptasiloxane; dioctyl terephthalate;Bis[2-(2-butoxyethoxy)ethyl]adipate (BBEEA); triethylene gylcolbis(2-ethylhexanoate) (TEG BEH); propylene carbonate (PC); triethyleneglycol monomethyl ether(methoxytriglycol); triethylene glycol monoethylether (ethoxytriglycol); tetraglyme; 18-Crown 6-Ether;1,3-dimethylimidazolidinone (DMI); poly(ethylene glycol)bis(2-ethylhexanoate); 1,5-pentanediol; di(ethylene glycol)dibenzoate;2-ethylhexyl-(s)-lactate; tripropylene glycol; dipropylene glycol;2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; tri(propyleneglycol)methyl ether, mixture of isomers (Dowanol™ TPM); di(propyleneglycol)dibenzoate; dipropylene glycol n-butyl ether; diethyl azelate;poly(propylene glycol)dibenzoate; propylene glycol phenyl ether;poly(ethylene glycol)dibenzoate; 2-ethyl-1,3-hexanediol; or the like.

One or more solvents may be present in a switching material in an amountfrom about 50% to about 95% (by weight), or any amount or rangetherebetween, for example 50, 60, 70, 80 or 90%, or any amount or rangetherebetween.

In some embodiments of the invention, one or more polymers may beincluded in the compositions. Examples of such polymers includepolyvinylbutyral (PVB) B-90, PVB-B72, poly(methyl methacrylate) (PMMA),nitrile rubber (NBR), polyvinylpyrrolidone (PVP), polyvinylidenefluoride (PVDF), poly(dimethylsiloxane) (PDMS), poly(ethyl methacrylate)(PEMA), NBR, hydroxypropyl cellulose, PEG-DMA (poly(ethyleneglycol)dimethacrylate), PHEMA (poly(2-hydroxyethyl methacrylate),Plexiglas™ G-UVT acrylic, polychloroprene, polybutadiene, PDMS-g-PEG(PEG-modified PDMS), PEO (polyethylene oxide), PEG-MEMA (PEG-methylethermethacrylate), PPGMA (poly(propylene glycol), EGDMA (ethylene glycoldimethacrylate), PVDC (polyvinylidene chloride), PVC (polychlorovinyl),PVDC-PVC, cyclo olefin copolymer (COC) (APEL™), carboxymethyl cellulose(CMC), SOLEF™ 21520, SOLEF™ 21508, zein, polyisobytulene-600,poly(ethylene-co-methacrylic acid (EMAA, SURLYN™ 60),polyethylene-co-(ethylacrylate), ethylacrylate, poly(vinylidenechloride-co-vinyl chloride), polyisoprene, polybutene, poly(sodium4-styrene sulfonate), HEMA (hydroxyethyl)methacrylate or combinationsthereof, or copolymers thereof. The one or more polymers may be presentin an amount from about 0.1% to about 10% (by weight) or any amount orrange therebetween, for example 1, 2, 3, 4, 5, 6, 7, 8, or 9%, or anyamount or range therebetween. In some embodiments the one or morepolymers may function as a rheology modifier.

Supporting electrolytes are generally electrically conductive, and maycomprise alkali metal salts, tetralkylammonium salts or the like.Examples of such salts include TBABF₄ (tetrabutylammoniumtetrafluoroborate), TBAPF₆ (tetrabutylammonium hexafluorophosphate),tetrabutylammonium perchlorate, lithium bis(trifluoromethanesulfonimide), triflate, LiBOB (lithium bis(oxatlato)borate), LiClO₄(lithium perchlorate) or the like. The one or more salts may be presentin an amount from about 0.1% to about 10% (by weight) or any amount orrange therebetween, for example 1, 2, 3, 4, 5, 6, 7, 8, or 9%.

In some embodiments of the invention, a charge compensator(charge-transfer complex or charge-transfer salt) may be included in oneor more compositions. A charge compensator may be a cathodic material toaid in redox balance of an anodic chromophore. The charge compensatormay be stable, or sufficiently stable in both reduced and oxidizedforms. The charge compensator may be an organic semiconductor. Examplesof charge compensators include Prussian Blue, ferroceniumtetrafluoroborate, ferrocenium hexafluorophosphate,tetracyanoquinodimethane, tetrafluoro-tetracyanoquinodimethane,1,4-dicyanobenzene, 1,2,4,5-tetracyanobenaene, pyrene, tetracene,pentacene or the like. The one or more charge compensators may bepresent in an amount from about 0.1% to about 10% (by weight) or anyamount or range therebetween, for example 1, 2, 3, 4, 5, 6, 7, 8, or 9%.

Inclusion of a colourant in a composition according to variousembodiments of the invention may achieve a desired colour and/or adjustthe visible light transmission of the composition. A variety ofcolourants are known in the art, and selection of a colourant to achievea desired colour, hue or transmissibility is within the ability of askilled worker. Examples of colourants include one or more chromophoresas described herein, Prussian blue, or the like. One or more colourantsmay be present in an amount from about 0.01% to about 10% (by weight) orany amount or range therebetween, for example 1, 2, 3, 4, 5, 6, 7, 8, or9%.

UV absorbers (compounds or compositions that absorb light and dissipateenergy by thermal relaxation) may be included in a composition accordingto various embodiments of the invention. Examples of UV blocking agentsinclude Biphenyl, 2-Hydroxybenzophenone,2,2′-Dihydroxy-4,4′-dimethoxybenzophenone, 2,4-Dihydroxybenzophenone,2-(2-Hydroxy-5-methylphenyl)benzotriazole, Ethyl2-cyano-3,3-diphenylacrylate,2-(2H-Benzotriazol-2-yl)-4,6-di-tert-pentylphenol,2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl), Hostavin™ VSU(N1-(2-ethoxyphenyl)-N2-(2-ethylphenyl)-ethanediamide) and the like. Oneor more UV absorbers may be present in an amount from about 0.01% toabout 10% (by weight) or any amount or range therebetween, for example1, 2, 3, 4, 5, 6, 7, 8, or 9%.

UV stabilizers, such as HALS (hindered amine light scavengers may beincluded in a composition according to various embodiments of theinvention. Examples of HALS include 2,2,6,6-tetramethyl-piperidine,2,2,6,6-tetramethyl-4-piperidinol, 1,2,2,6,6-pentamethyl-4-piperidinol,1,5,8,12-Tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazododecane,Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,Bis(1-octyloxyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate,Chimassorb™944(Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]]),HS-508 (Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; decanedioicacid bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester or the like. One ormore UV stabilizers may be present in an amount from about 0.01% toabout 10% (by weight) or any amount or range therebetween, for example1, 2, 3, 4, 5, 6, 7, 8, or 9%.

Uses

Compounds, and compositions or switching materials according to variousembodiments of the invention, may be useful in devices or applicationswhere an optical filter is employed. The compounds or compositions maybe used in films or coatings that may be applied to a surface such asglass, a lens or the like, and modify the light transmittance. Examplesof such devices include opthalmic lenses, actinometers, molecularsensors, photochromic inks, paints or fibers, variable transmissionfilters, optical information storage systems, optoelectronic systems,reversible holographic systems, molecular switches such as those used inmolecule-based Wires and circuitry or the like.

In some embodiments, the switching material may be disposed upon a firstsubstrate, or “sandwiched’ between a first substrate and a secondsubstrate, the switching material capable of transitioning between alight state and a dark state based on application of light in the UVand/or VIS range, and application of an electric voltage. Switchingmaterial disposed upon a substrate, with or without a second substrate,may be generally referred to an optical filter. The switching materialmay be a liquid, a gel, a solid, a semi-solid or a sol-gel, and may beformed in a layer with a thickness of about 0.1 micron (micrometer, μm)to about 100 microns, or any amount or range therebetween, for examplefrom about 10 microns to about 50 microns, or from about 0.1 micron toabout 10 microns, or from about 0.5 micron to about 5 microns, or anyamount or range therebetween. In some embodiments, the layer ofswitching material is of uniform, or substantially uniform, thickness.In some embodiments, the layer of switching material is of non-uniformthickness.

The first and/or second substrates may be independently opaque ortransparent, or substantially transparent. In some embodiments, when theswitching material is disposed upon, or sandwiched between thesubstrate(s), it is optically clear (e.g. demonstrating a haze of lessthan about 5%, less than about 4%, less than about 3%, less than about2% or less than about 1%. Haze may be measured using methods known inthe art, for exampley use of an XL-211 Hazemeter from BYK-Gardner,according to manufacturer's instructions.

In some embodiments, the first and/or second substrates may block(absorb or reflect) selected ranges or wavelengths of light. In someembodiments the first and/or second substrates may be treated with, orhave applied to them, a film or other material that blocks selectedranges or wavelengths of light. In some embodiments, the range orwavelength of light may be in the UV range. Examples of UV blockingfilms that may be applied include EnergyFilm™ (ArtScape) and EnerLogic™(Solutia).

In some embodiments, the optical filter may be disposed upon a pane ofglass, or other transparent material suitable for use as a window, orincorporation into an insulated glazing unit (IGU), or a storm window orsecondary glazing. Methods of making IGU, windows or the like, andaffixing an optical filter to glass or other suitable material aredescribed in, for example, WO2010/142019 as are methods of configuringan electrical system and/or control system for operation (electrofading)of an IGU comprising an optical filter.

In some embodiments, for a compound according to Formula IIA and IIB,where R₁ and R₂ are F, Z is S and X is S, at least one of R₆ or R₇ isnot H or not methyl, or not alkyl.

In some embodiments, for a compound according to Formula IIA and IIB,where R₁ and R₂ are F, Z is S and X is S, at least one of R₇ is notmethyl.

In some embodiments, for a compound according to Formula IIIA and IIIB,where R₁ and R₂ are F and Z is S, at least one of R_(8c) or R_(9c) isnot butyl, or not tert-butyl or not alkyl or not methoxy.

In some embodiments, for a compound according to Formula IIIA and IIIB,where R₁ and R₂ are F and Z is S, at least one of R₉ is Cl or both R₈ isCl.

In some embodiments, for a compound according to Formula IIIA and IIIB,where R₁ and R₂ are F, and Z is S, R_(9c) is not butyl, or nottert-butyl.

In some embodiments, for a compound according to Formula IA and IB,where R₁ and R₂ are F, Z is S and R4 is

R₃ is not

In some embodiments, for a compound according to Formula IA and IB,where R₁ and R₂ are F, Z is S and R₃ is

R₄ is not

In some embodiments, for a compound according to Formula IA and IB,where R₁ and R₂ are F and Z is S, R₃ and R₄ are not

In some embodiments, for a compound according to Formula VIIIA andVIIIB, where R₁ and R₂ are F and Z is O and all of R_(10a), R_(10b),R_(10c) and R_(10d) are H, R₉ in the para position (specifically R_(9a))is not an alkyl chain according to C₄H₉, C₈H₁₇ or C₁₂H₂₅.

In some embodiments, the invention does not include one or more of S001,S002, S006 S042, S054, S068 or S079. In some embodiments, the inventiondoes not include one or more of S003, S004, U008, S014 or S015, S033 orS075.

For all diarylethenes disclosed herein, where a ring-open isomer isillustrated, it is understood how the ring-closed isomer may be preparedfrom it; where a ring-closed isomer is illustrated, it is understood howthe ring-open isomer may be prepared from it.

The present invention also provides for an embodiment comprising anycombination of embodiments or aspects as referenced herein. Anyembodiment or aspect referenced in this specification may be implementedor combined with respect to any other embodiment, aspect, method,composition or use of the invention, and vice versa. Exemplaryembodiments of the invention are illustrated, in part, by the followingnon-limiting methods and examples:

General Methods

All solvents were dried prior to use; where necessary, solvents weredegassed by bubbling with argon or nitrogen. Alternately, solvents werepassed through a steel column containing activated alumina undernitrogen or argon using an MBRAUN solvent purification system. Solventsfor NMR analysis (Cambridge Isotope Laboratories) were used as received.Column chromatography was performed using silica gel 60 (230-400 mesh)from Silicycle Inc. Octafluorocyclopentene was purchased from SynQuestand catalysts Pd(dppf)Cl₂ and Pd(PPh₃)₄ were purchased from Strem. Allother synthetic precursors, solvents and reagents were purchased fromAldrich, Anachemia or Calcdon. ¹H NMR characterizations were performedon a Bruker AMX 400 instrument working at 400.103 MHz. ¹³C NMRcharacterizations were performed on a Bruker AMX 400 instrument workingat 100.610 MHz. Chemical shifts (δ) are reported in parts per millionrelative to tetramethylsilane (TMS) using the residual solvent peak as areference standard. Coupling constants (J) are reported in Hertz.Standard lamps for visualizing TLC plates (Spectroline E-series, 470μW/cm²) were used to carry out the ring-closing reaction for a compound,using a 365 nm, a 313 nm or a 254 nm light source where appropriate. Thecompositions of all photostationary states were detected using ¹H NMRspectroscopy. The ring-opening reactions were carried out using thelight of a 150 W tungsten source that was passed through a 490 nm or a434 nm cutoff filter to eliminate higher energy light.

Synthesis of Ring-Closed or Ring-Open Isomer of Compounds

Where a preparation of a ring-closed isomer is desired (as an isolatedcompound, e.g. for NMR studies, or some syntheses), the compound maybedissolved in CHCl₂ and placed in a quartz glass cell. The solution wasirradiated at 365 nm for 10 minutes, or until no further change inabsorbance is observed. Solvent was evaporated off under reducedpressure and the product purified using HPLC to afford the respectivering-closed isomer. Where a preparation of a ring-open isomer is desired(as an isolated compound, e.g. for NMR studies, or some syntheses), thecompound may be dissolved in CHCl₂ and placed in a quartz glass cell asdescribed. The solution may be irradiated with visible light comprisinga wavelength of ˜500 to 700 nm for 10 minutes, or until no furtherchange in absorbance is observed. Solvent may be evaporated off underreduced pressure and the product purified using HPLC to afford therespective ring-open isomer.

Photostationary State (PSS)

UV/Vis spectra are obtained using an OceanOptics™ Spectrophotometeruntil absorption in the visible region of the spectrum stabilizes. A2×10⁻⁵M solution of compound in solvent is prepared, and photofadedusing visible light until absorption in the visible region of thespectrum stabilizes. The sample is then irradiated with simulatedsunlight (QSUN SS-150 Solar Simulator with xenon arc lamp) until theabsorption spectrum stabilizes. To obtain PSS in the presence of a UVblocking film, a second sample is prepared and irradiated as described,with a UV blocking film inserted in the light path when irradiating.

Electrochemical Switching

A 1 mM solution of compound in solvent (triglyme, acetonitrile ordichloroethane) with 1% wt electrolyte (TBAPF₆ or TBAPF₄) was prepared,placed in a capillary device (50 micron wide chamber of two panes ofglass with ITO-coated interior walls, separated by a circumferentialbead of sealant; one of the two panes comprising two fill ports), andexposed to 365 nm UV light source until a PSS is reached. A voltage isapplied to the capillary device (from 0 to about 2, or from 0 to about2.5 volts), and the solution inspected visually for colorimetric changeto a faded state, indicating the chromophore exhibits electrochemicalswitching.

General Synthetic Methods:

General Procedure for Bi-Functional Kumada Coupling (Protocol A):

A reaction flask was charged with magnesium turnings (2.4 eq.) andanhydrous diethyl ether and flushed with argon. A small amount of thebromothiophene was added to initiate the reaction, followed by thedropwise addition of balance of the bromothiophene (2 eq. total) as asolution in anhydrous diethyl ether at such a rate as to maintain a mildreflux. After the addition was complete, the reaction was refluxed for afurther 30 minutes. The mixture was cooled to RT, and the liquid portionwas transferred to an addition funnel and added dropwise to a solutionof 2,3,5-tribromothiophene (1 eq.) and[1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (II)(Pd(dppf)Cl₂) (0.4 mol %) in anhydrous diethyl ether. The reactionmixture was stirred for 16 h at room temperature, then was poured overice and quenched with 5% HCl. The organic portion was separated and theaqueous layer was extracted with diethyl ether. The combined organicextracts were washed with brine, dried over MgSO₄, filtered and solventremoved by rotary evaporation. Flash chromatography afforded theproduct, which was sonicated in methanol, filtered and dried to give anoff-white powder.

General Procedure for Mono-Functional Kumada Coupling (Protocol B):

A reaction flask was charged with magnesium turnings (1.1 eq.) andanhydrous diethyl ether and flushed with argon. A small amount of thebromothiophene was added to initiate the reaction, followed by thedropwise addition of balance of the bromothiophene (1 eq. total) as asolution in anhydrous diethyl ether at such a rate as to maintain a mildreflux. After the addition was complete, the reaction was refluxed for afurther 30 minutes. The mixture was cooled to RT, and the liquid portionwas transferred to an addition funnel and added dropwise to a cooled (0°C.) solution of aryl bromide (1 eq.) and Pd(dppf)Cl₂ (0.5 mol %) inanhydrous diethyl ether. The reaction mixture was stirred for 1 h, thenwarmed to room temperature and stirred for 16 h. The reaction wasquenched by pouring it over ice and the mixture was acidified with 5%HCl. The organic portion was separated and the aqueous layer wasextracted with diethyl ether. The combined organic extracts were washedwith brine, dried over MgSO₄, filtered and solvent removed by rotaryevaporation. Flash chromatography afforded the product.

General Procedure for Bi-Functional Suzuki Coupling (Protocol C):

Sodium carbonate monohydrate (5 eq.) was dissolved in water and asolution of 2,3,5-tribromothiophene (1 eq.) and boronic acid (2.3 eq.)in THF was added. The reaction mixture was deoxygenated by bubblingargon through the solution for 60 minutes. Tetrakis(triphenylphosphine)palladium (0) (Pd(PPh₃)₄) (5 mol %) was added and the reaction mixturewas heated to reflux for 18 hours. After cooling to RT, the organic andaqueous phases were separated and the aqueous phase was extracted withEtOAc. The combined organics were washed with water, dried over MgSO₄,filtered and solvent removed by rotary evaporation. Flash chromatography(hexanes) afforded the desired compound.

General Procedure for Mono-Functional Suzuki Coupling (Protocol D):

Sodium carbonate monohydrate (3 eq.) was dissolved in water and asolution of aryl bromide (1 eq.) and aryl boronic acid (1.1 eq.) in THFwas added. The reaction mixture was deoxygenated by bubbling argonthrough the solution for 60 minutes. (Pd(PPh₃)₄) (2 mol %) was added andthe reaction mixture was heated to reflux for 2-48 hours. After coolingto RT, the organic and aqueous phases were separated and the aqueousphase was extracted with EtOAc. The combined organics were washed withwater, dried over MgSO₄, filtered and solvent removed by rotaryevaporation. Flash chromatography afforded the desired compound.

General Procedure for Friedel-Crafts Alkylation (Protocol E):

Aluminum chloride (1.2-1.5 eq.) was added to a stirred solution of thearomatic compound (1.0 eq.) and either tert-butyl chloride or t-butylbromide (1.5-4.0 eq.) in anhydrous DCM. The mixture was stirred forbetween 30 min and 60 h at room temperature, then poured into coldwater, mixed well and separated. The aqueous portion was extracted withDCM and the combined organics were washed with water, dried over MgSO₄,filtered and solvent removed by rotary evaporation. Flash chromatographyafforded the desired compound.

General Procedure for NBS Bromination (Protocol F):

The aryl compound (1 eq.) was dissolved in dichloromethane (DCM)(protocol F1), chloroform (protocol F2), tetrahydrofuran (THF) (protocolF3) or a mixture of DCM and THF (protocol F4). N-bromosuccinimide (1.1eq.) was added and the mixture stirred at room temperature for 1-24 h.The reaction was quenched by pouring it into a 1 M NaOH solution, andthe organic portion was separated. The aqueous portion was extractedwith dichloromethane and the combined organics were washed with water,dried over MgSO₄, filtered and solvent removed by rotary evaporation.Sonication of the residue in methanol, followed by filtration and dryingafforded the desired compound.

General Procedure for the Synthesis of Chromophores (Protocol G):

The aryl bromide (2.0 eq.) was dissolved in anhydrous diethyl ether andsolution was cooled to between −25° C. and −50° C. n-Butyl lithium (2.5M in hexanes, 2.2 eq.) was added and the reaction mixture was stirredfor 15 min. Octafluorocyclopentene (1.0 eq.) was added neat, and thereaction mixture was allowed to stir and warm slowly to room temperatureovernight, then was quenched by the addition of 10% HCl. The organicportion was separated and the aqueous portion was extracted with ether.The combined organic extracts were washed with brine, dried over MgSO₄,filtered and the solvent removed by rotary evaporation. The crudematerial was purified by column chromatography and the resultingmaterial was sonicated in methanol, filtered and air dried to afford thedesired compound.

General Procedure for the Synthesis of Chromophores (Ether): Protocol H.

The aryl bromide (2.0 eq.) was dissolved in anhydrous diethyl ether(protocol H1), anhydrous tetrahydrofuran (protocol H2) or a mixture ofanhydrous diethyl ether and anhydrous tetrahydrofuran (protocol H3) andthe solution was cooled to between −25° C. and −50° C. n-Butyl lithium(2.5 M in hexanes, 2.2 eq.) was added and the reaction mixture wasstirred for 15 min. A solution of octafluorocyclopentene (1.0 eq.) inthe reaction solvent was added over a period of 20-30 minutes. Thereaction mixture was allowed to stir and warm slowly to room temperatureovernight, and quenched by the addition of 10% HCl. The organic portionwas separated and the aqueous portion was extracted with ether. Thecombined organic extracts were washed with brine, dried over MgSO₄,filtered and the solvent removed by rotary evaporation. The crudematerial was purified by column chromatography and the resultingmaterial was sonicated in methanol, filtered and dried to afford thedesired compound.

General Procedure for Olefin Preparation (Protocol I):

To a substituted phenol (1 eq.) solution in DMSO (3.1 molar) was addedsodium hydroxide (2 eq.). The mixture was stirred until most of solidswere dissolved (an increase in the temperature was noted). The reactionmixture was allowed to cool down to ˜40° C. and 1,1,2-trichloroethene(1.08 eq.) was added dropwise over (the temperature of the reactionmixture was controlled to not pass the 60° C. at maximum). At the end ofaddition the reaction temperature reached 60° C., and then started todrop. The reaction was stirred and allowed to cool down for 1 h. Thereaction mixture temperature was cooled to ˜30° C. and was poured ontoice. The mixture was transferred to a separation funnel and washed withhexanes several times until extraction of the entire product wasachieved. The organic layer was then dried over anhydrous magnesiumsulfate and filtered through a plug of silica gel. Hexanes were removedto afford the pure product.

General Procedure for Benzofuran Cyclization (Protocol J):

Boronic acid (1.1 eq.), Pd₂ dba₃ (1.2 mol %),(oxybis(2,1-phenylene))bis(diphenylphosphine) (5 mol %), cesium fluoride(3 eq.) and cesium carbonate (3 eq.) were placed into a three-neck roundbottom flask, sealed with a septum and purged with argon for 20-30minutes. A solution of the olefin (1 eq.) in 1,4-dioxane (0.35 molar)was added. The solution was vigorously stirred and brought to reflux for48 hours. The reaction was cooled down to room temperature andpartitioned between water and ether. The layers were separated and theaqueous layer was extracted with ether once more. The combined organiclayers were washed with brine, dried with anhydrous magnesium sulfate,filtered and concentrated. The pure product was obtained either aftersonication in methanol or chromatography column.

General Synthetic Scheme for Compounds According to Formula XA/B

(Scheme 5), according to Protocols K1, K2. Only the ring-openconfiguration is shown; Scheme 4 illustrates both Formula XA and XB. Atleast one of R3 and R3′, or R4 and R4′, or R5 and R5′ are not identical.

General procedure for the synthesis of chromophores (Protocol K1, K2):

K1: A first aryl bromide (150) (1.0 eq.) was dissolved in anhydrousdiethyl ether and solution was cooled to between −25° C. and −50° C.n-Butyl lithium (2.5 M in hexanes, 1.1 eq.) was added and the reactionmixture was stirred for 15 min. Octafluorocyclopentene (1.0 eq.) wasadded neat, and the reaction mixture was allowed to stir and warm slowlyto room temperature overnight, then was quenched by the addition of 10%HCl. The organic portion was separated and the aqueous portion wasextracted with ether. The combined organic extracts were washed withbrine, dried over MgSO₄, filtered and the solvent removed by rotaryevaporation. The crude material was purified by column chromatographyand the resulting material was sonicated in methanol, filtered and airdried to afford intermediate (151).

K2: A Solution of a Second Aryl Bromide (152)

(1.0 eq.) was dissolved in anhydrous diethyl ether and solution wascooled to between −25° C. and −50° C.; n-Butyl lithium (2.5 M in hexanes1.1 eq) was added and the reaction mixture stirred for 10-15 minutes,and a solution of intermediate (151) (1.0 eq) in ether was added over 5minutes. The reaction mixture was stirred for 15 minutes, quenched withaddition of 10% HCl. The organic portion was separated and the aqueousportion was extracted with ether. The combined organic extracts werewashed with brine, dried over MgSO₄, filtered and the solvent removed byrotary evaporation. The crude material was purified by columnchromatography and the resulting material was sonicated in methanol,filtered and air dried to afford the desired compound.

Examples of compounds according to various embodiments of the inventionare referenced and set out herein. For clarity, only ring-open isomersare illustrated—ring-closed isomers may be produced by methods andschemes described herein and will be readily apparent upon considerationof the present specification, and are included in the instant disclosureas if each were individually set out herein.

Example 1 Synthesis of S0033′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-di-tert-butyl-2,2′:5′,2″-terthiophene)

Synthesis of 3′-bromo-2,2′:5′,2″-terthiophene (1)

(1) was prepared on 83 mmol scale (83% yield) according to protocol A.

Synthesis of 3′-bromo-5,5″-di-tert-butyl-2,2′:5′,2″-terthiophene (2)

(2) was prepared on 38.8 mmol scale (97% yield) according to protocol E.

Synthesis of S003 Compound (2)

S003 was prepared on 7 mmol scale (37% yield) according to protocol G.¹H NMR (400 MHz, CDCl3) δ ppm 6.85 (d, J=3.7, 2H), 6.70 (d, J=3.7, 2H),6.45 (q, J=3.7, 4H), 6.38 (s, 2H), 1.39 (s, 18H), 1.20 (s, 18H).

Example 2 Synthesis of S0053′-(2-(2,5-diphenylthiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-2,2′:5′,2″-terthiophene

Synthesis of S005

A solution of Compound (1) (0.39 g, 1.19 mmol) in anhydrous ether (50mL) at −20° C. was treated with n-BuLi (0.50 mL, 1.23 mmol, 2.5 Msolution in hexanes) dropwise over 10 minutes, then was stirred for anadditional 20 minutes before the addition of a solution of compound (7)(0.34 g, 0.79 mmol) in anhydrous ether (50 mL) via cannula. The reactionmixture stirred for 16 hours and during this time gradually warmed to10° C. The reaction was quenched with the addition of 5% HCl (aq) (30mL) and extracted with EtOAc (2×30 mL). The combined organic fractionswere washed with brine (30 mL) dried over MgSO₄, filtered andconcentrated onto silica gel. Purification by flash columnchromatography (95:5 hexanes/chloroform) followed by sonication of thesolid product in a mixture of ether and ethanol yielded 90 mg (17%yield) of S005. ¹H NMR (600 MHz, CDCl₃) δ 7.45-7.43 (m, 2H), 7.39 (t,J=7.6, 2H), 7.32 (t, J=7.3, 1H), 7.25 (dd, J=4.7, 1.5, 1H), 7.17-7.12(m, 3H), 7.09 (dd, J=5.1, 1.2, 1H), 7.03-7.00 (m, 4H), 6.78 (dd, J=5.1,3.5, 1H), 6.70 (dd, J=3.5, 1.2, 1H), 6.57 (s, 1H), 6.07 (s, 1H).

Example 3 Synthesis of S0065-(4-chlorophenyl)-3-(2-(2,5-diphenylthiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-2-phenylthiophene

Synthesis of 3-bromo-2,5-diphenylthiophene (4)

(4) was prepared on 67 mmol scale (77% yield) according to protocol C.

Synthesis of 2,3-dibromo-5-(4-chlorophenyl)thiophene (5)

(5) was prepared on 19.7 mmol scale (23% yield) according to protocol C.

Synthesis of 3-bromo-5-(4-chlorophenyl)-2-phenylthiophene (6)

(6) was prepared on 32.1 mmol scale (78% yield) according to protocol C.

Synthesis of 3-(perfluorocyclopent-1-en-1-yl)-2,5-diphenylthiophene (7)

In a flame-dried, 2 L, 3-neck, rbf fitted with an argon inlet andinternal thermometer, 3-bromo-2,5-diphenylthiophene (21.0 g, 66.6 mmol)was dissolved in anhydrous THF (300 mL) and anhydrous ether (400 mL) wasadded. The solution was cooled to −43° C. (dry ice/acetone) and n-BuLi(2.5 M in hexanes, 32.0 mL, 80 mmol) was added dropwise over a period of10 minutes. A yellow colour was observed. The temperature increased to−40° C. and the reaction mixture was stirred for 15 minutes. A whiteprecipitate was observed. Octafluorocyclopentene (10.7 mL, 80 mmol) wasadded in one portion, and the temperature increased to −24° C. Thetemperature gradually decreased to −38° C. and the reaction mixture wasstirred until the temperature reached −5° C. (3 hours). The reaction wasquenched by the addition of 10% HCl (15 mL) and the mixture was pouredinto water (300 mL). The organic phase was separated and the aqueousphase extracted with EtOAc (150 mL). The combined organics were washedwith water (2×500 mL), dried over MgSO₄, filtered and solvent removed byrotary evaporation. The resulting brown slurry was sonicated with MeOH(50 mL) and filtered to afford a yellow powder (2.30 g). The filtratewas redissolved in DCM and dry-loaded onto silica gel. Flashchromatography (hexanes) afforded (7) as a clear, colourless oil, 20.7 g(73%).

Synthesis of S006

In a flame dried, 1 L, 3-neck, rbf equipped with a stirbar and an argoninlet, (6) (10.67 g, 30.5 mmol) was dissolved in anhydrous THF (150 mL)and anhydrous diethyl ether (250 mL) was added. The reaction mixture wascooled to −40° C. and n-BuLi (2.5 M in hexanes, 15.3 mL) was addeddropwise over a period of 10 minutes. The resulting yellow solution wasallowed to stir for 10 minutes. A solution of (7) (13.07 g, 30.5 mmol)in anhydrous THF (100 mL) was added via cannula over a period of 5minutes. The temperature of the reaction increased to −28° C. and slowlycooled back down to −40° C. The reaction was allowed to stir until theinternal temperature reached −12° C. The reaction was quenched by theaddition of 10% HCl (15 mL) and was poured into water (200 mL) and mixedwell. The aqueous phase was separated and extracted with EtOAc (250 mL).The combined organics were washed with water (500 mL), dried over MgSO₄,filtered and solvent removed by rotary evaporation. Flash chromatographySilica gel, (hexanes to 2% EtOAc/hexanes) afforded a yellow, powderysolid, two fractions: F1: 5.57 g (26.9%) and F2: 6.08 g (29.3%). ¹H NMR(400 MHz, CDCl₃) δ 7.38-7.28 (m, 9H), 7.10-7.07 (m, 6H), 7.02-6.97 (m,4H), 6.28 (s, 1H), 6.25 (s, 1H).

Example 4 Synthesis of S0073′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-dimethyl-2,2′:5′,2″-terthiophene)

Synthesis of S007

S007 was prepared on 3.6 mmol scale (51% yield) according to protocol G.¹H NMR (400 MHz, CDCl₃) δ 6.86 (d, J=3.5 Hz, 2H), 6.65 (dd, J=3.5, 1.1Hz, 2H), 6.46 (dt, J=3.5, 2.3 Hz, 4H), 6.33 (s, 2H), 2.49 (d, J=0.7 Hz,6H), 2.20 (d, J=0.7 Hz, 6H).

Example 5 Synthesis of S0113′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(4,4″,5,5″tetramethyl-2,2′:5′,2″-terthiophene

Synthesis of 5-bromo-2,3-dimethylthiophene (8)

To a solution of 2,3-dimethylthiophene (21.68 g, 192 mmol) in glacialacetic acid (20 mL) was added N-bromosuccinimide (NBS) (34.39 g, 192 mg)over 5 minutes (the temperature increased to 50° C.). The reaction wascomplete (TLC: hexanes) after 10 minutes then poured over ice. Oncecooled, the organics were extracted with DCM and the combined fractionswere washed with 1M NaOH, water and brine. The resulting solution wasdried with MgSO₄, concentrated under vacuum to yield a light orange oil.Flash chromatography afforded 8 (19.07 g, 52%). ¹H NMR (600 MHz, CDCl₃)δ 6.72 (s, 1H), 2.27 (s, 3H), 2.09 (s, 3H).

Synthesis of 3′-bromo-4,4″,5,5″-tetramethyl-2,2′:5′,2″-terthiophene (9)

(9) was prepared on 3.9 mmol scale (30% yield) according to protocol A.¹H NMR (600 MHz, CDCl₃) δ 7.09 (s, 1H), 6.93 (s, 1H), 6.85 (s, 1H), 2.36(s, 3H), 2.34 (s, 3H), 2.15 (s, 3H), 2.12 (s, 3H).

Synthesis of S011

S011 was prepared on 0.27 mmol scale (20% yield) according to protocolH2. ¹H NMR (400 MHz, CDCl3) δ 6.74 (s, 2H), 6.34 (s, 4H), 2.34 (s, 6H),2.11 (s, 6H), 2.08 (s, 6H), 1.85 (s, 6H).

Example 6 Synthesis of S012 methyl4′-(2-([2,2′:5′,2″-terthiophen]-3′-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-[2,2′:5′,2″-terthiophene]-5-carboxylate

To a 100 mL round bottom flask was added S047 (32 mg, 0.055 mmol),toluene (20 mL), MeOH (5 mL) and concentrated H₂SO₄ (0.2 mL). The flaskwas fitted with a Dean Stark trap and the mixture was heated to refluxfor 18 hours. After cooling the reaction mixture was diluted with water(20 mL) and extracted with DCM (2×20 mL). The combined organic fractionswere washed with brine, dried with MgSO₄ and concentrated onto silicagel. The crude product was purified by flash column chromatography (9:1hexanes/EtOAc) to yield 19 mg of S012. ¹H NMR (600 MHz, CDCl₃) δ 7.70(d, J=3.9, 1H), 7.28-7.25 (m, 1H), 7.18 (dd, J=5.1, 1.2, 1H), 7.16 (dd,J=5.1, 1.2, 1H), 7.07 (dd, J=3.6, 1.1, 1H), 7.05-7.01 (m, 2H), 6.84-6.81(m, 2H), 6.73 (dd, J=3.6, 1.2, 1H), 6.71 (dd, J=3.5, 1.2, 1H), 6.46 (s,1H), 6.37 (s, 1H), 3.92 (s, 3H).

Example 7 Synthesis of S013 2-(2-(2-ethoxyethoxy)ethoxy)ethyl4′-(2-([2,2′:5′,2″-terthiophen]-3′-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-[2,2′:5′,2″-terthiophene]-5-carboxylate

To a 50 mL round bottom flask was added S047 (28 mg, 0.039 mmol),triethylene glycol monoethyl ether (50 mg, 0.08 mmol), DCC (17 mg, 0.08mmol), DMAP (10 mg, 0.08 mmol) and DCM (15 mL). The reaction mixturestirred under Ar for 42 hours. The reaction mixture was then filtered bygravity, diluted with water (10 mL) and extracted with DCM (2×10 mL).The combined organic fraction were washed with brine (10 mL), dried overMgSO₄ and concentrated onto silica gel. The crude product was purifiedby flash column chromatography to yield 13 mg of S013. ¹H NMR (600 MHz,CD₂Cl₂) δ 7.72 (d, J=3.9, 1H), 7.30 (dd, J=5.1, 1.2, 1H), 7.22 (dd,J=5.1, 1.2, 1H), 7.20 (dd, J=5.1, 1.3, 1H), 7.11 (dd, J=3.6, 1.2, 1H),7.08 (d, J=3.9, 1H), 7.06-7.03 (m, 1H), 6.85-6.81 (m, 2H), 6.77-6.74 (m,1H), 6.74-6.71 (m, 1H), 6.52 (s, 1H), 6.41 (s, 1H), 4.47-4.42 (m, 2H),3.83-3.78 (m, 2H), 3.70-3.66 (m, 2H), 3.65-3.62 (m, 2H), 3.62-3.58 (m,2H), 3.56-3.52 (m, 2H), 3.48 (q, J=7.0, 2H), 1.17 (t, J=7.0, 3H).

Example 8 Synthesis of S0143,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-phenylbenzo[b]thiophene)

Synthesis of 2,3-dibromobenzo[b]thiophene (10)

A solution of 18 g (134 mmol) of benzo[b]thiophene in 200 mL ofchloroform was stirred and to this mixture was added 42.9 g (13.7 mL,268 mmol) of bromine in 100 mL of chloroform dropwise at RT over 1.5 h.After stirring for 18 h, solid NaHCO₃ was added to neutralize thehydrobromic acid. The organic layer was washed with water and Na₂S₂O₈and dried (MgSO₄). On evaporation of the solvent solid was obtainedwhich was crystallized from methanol to give 38.8 g (99%) of2,3-dibromobenzo[b]thiophene.

Synthesis of 3-bromo-2-phenylbenzo[b]thiophene (11)

(11) was prepared on 31 mmol scale (77% yield) yield according toprotocol D.

Synthesis of S014

S014 was prepared on 0.72 mmol scale (15% yield according to protocolH2. ¹H NMR (600 MHz, CD₂Cl₂) δ 7.65 (d, J=8.0 Hz, 1H), 7.23-7.17 (m,1H), 7.04-6.96 (m, 2H), 6.91-6.83 (m, 4H), 6.81 (d, J=8.2 Hz, 1H).

Example 9 Synthesis of S0174,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(3-methyl-2,5-diphenylthiophene)

Synthesis of 3-bromo-4-methyl-2,5-diphenylthiophene (12)

(12) was prepared on 8.1 mmol scale (68% yield) according to protocol C.¹H NMR (600 MHz, CDCl₃) δ 7.71-7.68 (m, 2H), 7.50-7.43 (m, 6H),7.41-7.36 (m, 2H), 2.36 (s, 3H).

Synthesis of S017

S017 was prepared on 0.25 mmol scale (17% yield) according to protocolG. ¹H NMR (600 MHz, CDCl₃) δ 7.47-7.41 (m, 4H), 7.39-7.34 (m, 6H),7.19-7.15 (m, 2H), 7.15-7.10 (m, 4H), 7.10-7.06 (m, 4H), 1.14 (s, 3H),1.13 (s, 3H).

Example 10 Synthesis of S0193′,3″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-dibromo-2,2′:5′,2″-terthiophene)

Synthesis of S019

To a solution of S001 (2.0 g, 3 mmol) (U.S. Pat. No. 7,777,055) in DCM(50 mL) and acetic acid (50 mL) was added a solution of bromine (0.61mL, 12 mmol) in acetic acid (30 mL) drop-wise over 30 minutes (reactionprogress monitored by TLC-hexanes/DCM 9:1). The reaction was stirred for16 hours then filtered. Traces of acetic acid were removed under highvacuum. The resulting yellow solid was triturated with cold diethylether, filtered and dried, yielding S019 (2.24 g, 76%) as a brightyellow solid. ¹H NMR (600 MHz, CDCl₃) δ 6.99 (d, J=3.9 Hz, 2H), 6.89 (d,J=3.8 Hz, 2H), 6.78 (d, J=3.8 Hz, 2H), 6.44 (s, 2H), 6.42 (d, J=3.8 Hz,2H).

Example 11 Synthesis of S0203′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-dimethoxy-2,2′:5′,2″-terthiophene)

Synthesis of 3′-bromo-5,5″-dimethoxy-2,2′:5′,2″-terthiophene (13)

A mixture of 2-methoxythiophene (5.00 g, 43 mmol), potassium acetate(2.58 g, 26.3 mmol), tetrabutylammonium bromide (2.82 g, 8.76 mmol),palladium(II)acetate (0.10 g, 0.87 mmol), and 2,3,5-tribromothiophene(1.26 g, 3.93 mmol) in DMF (100 mL) was heated to 80° C. for two hours.Once the reaction was complete (TLC: 10% EtOAc in hexanes), it wascooled and the organics were extracted with DCM. Combined fractions werewashed with 1 M NaOH, water, then brine. The resulting solution wasdried with MgSO₄, concentrated under vacuum to afford a dark oil. Flashchromatography afforded 13 (0.88 g, 69%) as a yellow solid. ¹H NMR (600MHz, CDCl₃) δ 7.02 (d, J=4.0 Hz, 1H), 6.85 (s, 1H), 6.79 (d, J=4.0 Hz,1H), 6.18 (d, J=4.0 Hz, 1H), 6.12 (d, J=4.0 Hz, 1H), 3.93 (s, 3H), 3.91(s, 3H).

Synthesis of S020

S020 was prepared on 1.88 mmol scale (38% yield) according to protocolH2. ¹H NMR (600 MHz, CDCl3) δ 6.71 (d, J=3.9 Hz, 2H), 6.38 (s, 2H), 6.31(d, J=3.9 Hz, 2H), 6.12 (d, J=3.9 Hz, 2H), 5.90 (d, J=3.9 Hz, 2H), 3.91(s, 6H), 3.68 (s, 6H). ¹³C NMR (151 MHz, CDCl₃) δ 167.92, 166.14,137.41, 135.73, 124.53, 124.28, 122.93, 122.35, 121.93, 119.04, 104.61,104.51, 60.55, 60.04, 29.92.

Example 12 Synthesis of S024 3′,3′″-(perfluorocyclopent-1-ene-1,2diyl)bis(([2,2′:5′,2″-terthiophene]-5,5″-dicarboxylic acid)

In a flame-dried 250 mL rbf, diisopropylamine (3.0 mL, 21.7 mmol) wasadded to anhydrous THF (30 mL), and cooled to 0° C. n-BuLi (2.5 M inhexanes, 7.9 mL, 19.7 mmol) was added dropwise over a period of 5minutes. The reaction mixture was allowed to stir at 0° C. for 30minutes and then added dropwise to a solution of S001 (3.00 g, 4.49mmol) in anhydrous THF (30 mL) at 0° C. Upon addition, an immediate redcolour was observed, and over time a brown precipitate formed. The brownslurry was allowed to stir at 0° C. for 90 minutes, then was cooled to−78° and quenched by bubbling CO₂ through the solution for 2 hours. Thecooling bath was removed and the reaction mixture allowed to slowly warmto RT while bubbling was continued overnight. The reaction was quenchedby the addition of methanol (20 mL), and the mixture was poured intowater (200 mL) and extracted with a mixture of THF/EtOAc (1:1, 2×100mL). The combined organics were washed with water (200 mL), dried overMgSO₄, filtered and solvent removed by rotary evaporation to afford ayellow/green, flaky solid, 3.17 g (84%). ¹H NMR (400 MHz, DMSO) δ 7.65(d, J=3.9 Hz, 2H), 7.45 (d, J=3.9 Hz, 2H), 7.36 (d, J=3.9 Hz, 2H), 6.86(d, J=3.8 Hz, 2H), 6.70 (s, 2H).

Example 13 Synthesis of S0263′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-dichloro-2,2′:5′,2″-terthiophene)

Synthesis of 3′-bromo-5,5″-dichloro-2,2′:5′2″-terthiophene (14)

(14) was prepared on 9.2 mmol scale (54% yield) according to protocol A.¹H NMR (600 MHz, CDCl₃) δ 7.15 (d, J=4.0, 1H), 6.99 (s, 1H), 6.94 (d,J=3.9, 1H), 6.90 (d, J=4.0, 1H), 6.86 (d, J=3.9, 1H).

Synthesis of S026

S026 was prepared on 0.074 mmol scale (6% yield) according to protocolG. ¹H NMR (600 MHz, CDCl₃) δ 6.89 (d, J=3.9, 2H), 6.86 (d, J=3.9, 2H),6.65 (d, J=3.8, 2H), 6.47-6.44 (m, 4H).

Example 14 Synthesis of S0273′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methyl-2,2′:5′,2″-terthiophene)

Synthesis of 3-bromo-5′-methyl-2,2′-bithiophene (15)

(15) was prepared on 98 mmol scale (94% yield) according to protocol B.¹H NMR (CDCl₃, 600 MHz) δ 7.22 (d, J=3 Hz, 1H), 7.16 (d, J=5 Hz, 1H),7.00 (d, J=5 Hz, 1H), 6.75 (d, J=3 Hz, 1H). 2.52 (s, 3H).

Synthesis of 3,5-dibromo-5′-methyl-2,2′-bithiophene (16)

N-Bromosuccinimide (15.55 g, 87 mmol) was added portionwise to stirredsolution of 3-bromo-5′-methyl-2,2′-bithiophene (20.56 g, 79 mmol) inglacial acetic acid (200 mL) containing acetic anhydride (25 mL) at RT.The mixture was stirred and monitored by TLC. After completion (1.5 h)the reaction was diluted with water (200 mL) and the oily phase wastaken into ether and separated. The aqueous phase was extracted withether. The combined organic phases were washed with 1 M NaOH solutionfollowed by water. Removal of the solvent left a solidifying oil, whichwas sonicated in methanol yielding after filtration and drying3,5-dibromo-5′-methyl-2,2′-bithiophene as off-white solid (single spoton TLC). Yield: 20.6 g (77%). ¹H NMR (600 MHz, CD₂Cl₂) ppm 7.13 (d,J=3.6 Hz, 1H), 6.97 (s, 1H), 6.74-6.72 (m, 1H), 2.48-2.47 (m, 3H)

Synthesis of 3′-bromo-5-methyl-2,2′:5′,2″-terthiophene (17)

(17) was prepared on 36 mmol scale (91% yield) according to protocol B.

Synthesis of S027

S027 was prepared on 3.76 mmol scale (8% yield) according to protocol G.¹H NMR (600 MHz, CDCl₃) δ ppm 7.30-7.28 (m, 2H), 7.18 (dd, J=5.1, 1.1Hz, 2H), 7.10 (dd, J=3.6, 1.1 Hz, 2H), 7.05 (dd, J=5.1, 3.6 Hz, 2H),6.85 (dd, J=5.1, 3.6 Hz, 2H), 6.74 (dd, J=3.6, 1.1 Hz, 2H), 6.40 (s,2H).

Example 15 Synthesis of S0322,2′,2″,5,5″-pentaphenyl-4,4′:5′,4″-terthiazole

Synthesis of 5-bromo-2-phenylthiazole (18)

Chloroacetic acid (43.7 g, 463 mmol) was ground in a mortar and pestleand added to thiobenzamide (63.5 g, 463 mmol) in a 1 L beaker. The twosolids were stirred manually and heated to 100° C. in an oil bath. At abath temperature of about 75° C., the mixture melted and an exothermicreaction ensued. The internal reaction temperature reached 115° C. Themixture was rigorously stirred at this temperature for 10 minutes.During this time the melt turned black and a gas was evolved (steam andHCL perhaps). The mixture was then cooled to room temperature andacetone (100 mL) was added. The viscous melt was carefully stirred up inacetone to produce a yellow suspension that was filtered andre-suspended in H₂O (500 mL). The suspension was extracted with Et₂O(4×400 mL). The ether fractions were combined and washed with brine,dried over MgSO₄ and concentrated to give a pale yellow solid (36.0 g).The crude product (35.9 g, 202.6 mmol) was used as-is, and transferredto a 1 L rbf; to this was added Bu₄NBr (78.17 g, 242.5 mmol) followed byP₂O₅ (69.0 g, 486.24 g) and toluene (500 mL). The mixture was heated at100° C. for 18 hours and cooled to room temperature. The top layer wasdecanted off and fresh toluene (300 mL) was added and the mixture againheated to 100° C. for 5 hours. The mixture was cooled, to roomtemperature and the top layer decanted. Another 300 mL of toluene wasadded to the mixture, heated at 100° C. in an oil bath for 20 hours.After cooling to room temperature, the top layer was decanted off. Thecombined toluene layers were vacuum-filtered to remove precipitates andthe filtrate washed with brine (4×200 mL). The organic layer was driedover MgSO₄, filtered and concentrated onto Silica gel and purified bycolumn (1:1 hexanes/CHCl₃). Two sets of fractions were collected (24.5 gand 3.0 g), both are the product but the later fraction had a strongyellow brown colouration. ¹H NMR (600 MHz, CDCl₃) δ 7.95-7.90 (m, 2H),7.47-7.42 (m, 3H), 7.21 (s, 1H).

Synthesis of 4,5-dibromo-2-phenylthiazole (19)

Compound 18 (5.0 g, 21 mmol) was dissolved in CHCl₃ (250 mL). Br₂ (16.7g, 105 mmol) was dissolved in CHCl₃ (50 mL) and added to the solution of18 via addition funnel over 10 minutes. The reaction mixture stirred atroom temperature for 5.5 hours; then was transferred to a 1 L separatoryfunnel and washed with Na₂S₂O₃ (3×100 mL) followed by brine (2×150 mL).The organic fractions were dried over MgSO₄ and concentrated. The crudeproduct was purified by column (2:1 hexanes/CHCl₃). ¹H NMR (600 MHz,CDCl₃) δ 7.85 (d, J=7.3, 2H), 7.50-7.40 (m, 3H).

Synthesis of 2,2′,2″-triphenyl-4,4′:5′,4″-terthiazole (20)

Compound 23 (2.0 g, 8.33 mmol) was weighed into a 250 mL rbf anddissolved in ether (100 mL). The thiazole was fully soluble at roomtemperature but precipitated out at −78° C. The mixture was warmed backto room temperature to re-dissolve Compound 2 and then cooled to −25° C.n-BuLi (3.5 mL, 8.75 mmol, 2.5 M solution in hexanes) was added dropwiseover 15 minutes and allowed to stir for an additional 30 minutes. Thelithiation was determined to be complete by TLC (1:1 hexane/CHCl₃). Thereaction was cooled to −50° C. and B(OBu)₃ was added all in one portion.The solid precipitate dissolved within 5-10 minutes (monitored byTLC—only a baseline spot was observed). The reaction mixture wasconcentrated and re-dissolved in THF (50 mL). Compound 19 (1.3 g, 4.2mmol) was dissolved into the mixture, 20% Na₂CO₃ (aq) (50 mL) was addedand the mixture de-oxygenated by bubbling Ar through for 30 minutes.Pd(PPh₃)₄ (0.30 g, 0.25 mmol) was added and the mixture refluxed for 16hours (overnight). After cooling to room temperature the layers wereseparated and the aqueous fraction extracted with EtOAc (2×50 mL). Thecombined organic fractions were washed with brine, dried over MgSO₄, andconcentrated onto Silica gel. The crude product (210 mg) was purified bycolumn (1:1 hexanes/CHCl₃). The photochromic product was usedimmediately in the next step without characterization.

Synthesis of 5,5″-dibromo-2,2′,2″-triphenyl-4,4′:5′,4″-terthiazole (21)

Compound 4 (220 mg, 0.46 mmol) was dissolved in CHCl₃ (100 mL). Br₂ (0.3g, 1.9 mmol) was dissolved in CHCl₃ (20 mL) and added to the reactionmixture dropwise over 30 minutes. The bromine colour did not immediatelydissipate when added to the starting material solution. The reactionmixture stirred at room temperature for 15 hours, and washed with of 5%Na₂S₂O₃ (aq) (50 mL), followed by brine (50 mL) and dried over MgSO₄,filtered and concentrated. The crude mixture (260 mg) was used in thenext step without further purification or characterization.

Synthesis of S032

Phenyl boronic acid (0.18 g, 1.5 mmol) was added to a 250 mL rbfcontaining of 20% Na₂CO₃ (50 g) and 50 mL THF. The mixture wasde-oxygenated by bubbling Ar through for 30 minutes. The deoxygenatedmixture was transferred via cannula to a second 250 mL rbf containingCompound 4 (0.29 g, 0.46 mmol). Pd(PPh₃)₄ (20 mg) was added, andrefluxed under Ar gas for 6 hours. After cooling to room temperature,the layers were separated and the aqueous extracted with EtOAc (2×30mL). The combined organic fractions were washed with brine, dried overMgSO₄ and concentrated. The crude product (160 mg) was purified bycolumn (9:1 hexanes EtOAc) followed by trituration from methanol. ¹H NMR(600 MHz, CDCl₃) δ 8.02-7.95 (m, 2H), 7.82-7.75 (m, 4H), 7.47-7.36 (m,9H), 7.15-7.09 (m, 8H), 7.08-7.03 (m, 1H), 7.02-6.98 (m, 1H).

Example 16 Synthesis of S034 3′,3′″″-(perfluorocyclopent-1-ene-1,2diyl)bis(5,5′″-dimethyl-2,2′:5′,2″:5″,2″′-quaterthiophene)

Synthesis of3′,3″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5″-bromo-5-methyl-2,2′:5′,2″-terthiophene)(22)

To a solution of S027 (1.9 g; 2.76 mmol) in the mixture of acetic acid(20 mL) and DCM (20 mL) was added at stirring bromine (0.93 g; 5.8 mmol)as a solution in acetic acid (7.5 mL). The mixture was stirred at RT for1 h then poured into 1 M NaOH solution and extracted with DCM. Organicphase was washed with 1 M NaOH and water, separated and concentratedunder vacuum. Flash chromatography (hexanes/DCM 9:1) afforded 22 (2.3 g,98% yield).

Synthesis of S034

S034 was prepared on 0.35 mmol scale (55% yield) according to protocolC. ¹H NMR (600 MHz, CDCl₃) δ 6.97 (d, J=3.8 Hz, 2H), 6.82 (d, J=4.0 Hz,2H), 6.50-6.48 (m, 4H), 6.36 (s, 2H), 2.25-2.23 (m, 6H).

Example 17 Synthesis of S0354,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-diphenylthiazole)

Synthesis of 4-bromo-2,5-diphenylthiazole (23)

(23) was prepared on 6.2 mmol scale (98% yield) according to protocol D.¹H NMR (600 MHz, CDCl₃) δ 7.99-7.93 (m, 2H), 7.73-7.68 (m, 2H),7.50-7.40 (m, 6H).

Synthesis of S035

S035 was prepared on 0.26 mmol scale (17.6% yield) according to protocolG. ¹H NMR (600 MHz, CDCl₃) δ 7.73-7.67 (m, 4H), 7.46-7.39 (m, 6H),7.14-7.08 (m, 4H), 7.08-7.04 (m, 4H), 7.01-6.95 (m, 2H)

Example 18 Synthesis of S036

Synthesis of 5-methyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (24)

2,2,6,6-Tetramethylpiperidine (HTMP, 8.20 g, 58.0 mmol) was dissolved indry THF (100 mL) in a septum sealed 250 mL rbf that had previously beenflushed with argon. The mixture was cooled in a dry ice/acetone bath for20 min; tert-BuLi (35.0 mL of a 1.7 M solution in pentane, 59.5 mmol)was added dropwise by syringe, and the reaction mixture was stirred for45 min, forming a precipitate. 3,4-Ethylenedioxythiophene (EDOT) (7.82g; 55 mmol) was added by syringe, and the mixture was stirred for 45 minto clarify. Iodomethane (12.5 g, 88.0 mmol) was added dropwise bysyringe, and the mixture was stirred for 30 min, after which the coolingbath was removed and the mixture stirred overnight. HCl (2 M, 80 mL) wasadded to quench the reaction. The mixture was swamped with diethyl ether(120 mL) and washed with saturated sodium hydrogen carbonate solution(80 mL) and saturated NaCl solution (80 mL). The organic phase was driedover anhydrous MgSO₄, filtered through a plug of silica gel andevaporated providing 8.35 g (97% yield) of methylated product. Theproduct was kept in ether/hexanes solution; to use in synthesis, 100 gof DMF was loaded into 500 mL rbf and the ether/hexane solution of (24)was added to the DMF and evaporated under vacuum. The DMF solution isclear and colourless and was used in the coupling reaction.

Synthesis of5,5′-(3-bromothiophene-2,5-diyl)bis(5-methyl-2,3-dihydrothieno[3,4-b][1,4]dioxine(25)

To a stirred solution of 3,4-ethylenedioxy-5-methylthiophene (7.5 g, 48mmol) in DMF (100 g) in argon flushed flask was added2,3,5-tribromothiophene (7.3 g, 22.7 mmol), potassium acetate (8.9 g, 90mmol), tetrabutylammonium bromide (14.7 g, 45.5 mmol), and palladiumacetate (1.0 g, 4.55 mmol). The mixture was heated to 80° C. withstirring and the reaction was monitored by TLC. After 1.5 h the reactionwas cooled and EtOAc (200 mL) and water (200 mL) were added. Afterseparation, the organic layer was evaporated to dryness and the blacktarry residue was loaded on silica gel. The product was isolated byflash chromatography using hexanes/EtOAc gradient (10 to 30% EtOAc) togive target product as an orange solid (4.23 g, 8.97 mmol, 39% yield).¹H NMR (600 MHz, CDCl₃) δ 7.01 (d, J=2.3 Hz, 1H), 4.33-4.29 (m, 4H),4.23 (m, 4H), 2.27 (d, J=3.3 Hz, 3H), 2.25 (s, 3H).

Synthesis of S036

S036 was prepared on 1.73 mmol scale (42% yield) according to protocolH3. ¹H NMR (600 MHz, CDCl₃) δ 6.69 (s, 2H), 4.33-4.28 (m, 4H), 4.25-4.21(m, 4H), 4.16-4.09 (m, 8H), 2.25 (s, 6H), 1.89 (s, 6H).

Example 19 Synthesis of S0374″,4″″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(([2,2′:5′,2″:5″,2″′-quaterthiophene]-5-carbonitrile))

Synthesis of S037

S037 was prepared on 0.27 mmol scale (54% yield) according to protocolC. ¹H NMR (600 MHz, CDCl₃) δ 7.56 (d, J=3.9 Hz, 2H), 7.22-7.18 (m, 4H),7.16 (d, J=3.8 Hz, 2H), 7.02 (d, J=3.7 Hz, 2H), 6.87-6.84 (m, 2H), 6.74(d, J=3.2 Hz, 2H), 6.40 (d, J=9.1 Hz, 2H).

Example 20 Synthesis of S038(E)-4′,4″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-((E)-styryl)-2,2′:5′,2″-terthiophene)

Synthesis of4′,4″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(([2,2′:5′,2″-terthiophene]-5-carbaldehyde))(26)

A solution of S001 (1.12 mmol, 0.75 g) and DMF (3.36 mmol, 0.25 g) indry dichloroethane (10 mL) was purged with argon and cooled to 0° C.Phosphoryl chloride (2.47 mmol, 0.38 g) was slowly added and thereaction mixture was stirred for 1 h at 0° C. The temperature was raisedto 20° C. for 16 h. Excess of DMF and POCl₃ (4 equiv.) was added and thereaction was continued for 6 days at RT. Yellow solid graduallyprecipitated and the spot of starting S001 was consumed (TLC). Themixture was poured into a potassium acetate solution (20 mL, 1 M) andvigorously stirred for 1 h at RT. The green mixture was extracted withDCM and the combined organic layers were dried over MgSO₄. The solventswere removed and two products were isolated by flash chromatography(hexanes) as yellow crystals. ¹H NMR (600 MHz, CDCl₃) δ ppm 9.90 (s,2H), 7.68 (d, J=3.9, 2H), 7.20 (dt, J=5.0, 1.5, 2H), 7.14 (d, J=3.9,2H), 6.85 (dd, J=5.1, 3.6, 2H), 6.75 (dd, J=5.1, 3.6, 1.2, 2H), 6.53 (s,2H).

Synthesis of S038

A mixture of benzyltriphenylphosphonium bromide (0.72 g, 1.66 mmol) and26 (0.40 g, 0.55 mmol) was dispersed in anhydrous THF (30 mL) andstirred at RT under argon atmosphere for 15 min. A solution of potassiumtert-butoxide (0.25 g, 2.23 mmol) in anhydrous THF (8 mL) was addeddropwise. The reaction mixture was stirred at RT for 45 min. Then waterwas added, followed by extraction with DCM (50 mL×3). The combinedextracts were dried over anhydrous sodium sulfate. Solvents were removedby rotary evaporation, followed by column chromatography (Silica gel;hexanes/DCM (9:1)), to yield a yellow solid (0.245 g; 51% yield) of thetarget product. More of product (0.082 g) was isolated in a separatefraction. Overall yield 68%. Additional purification by means ofcrystallization was done using diethyl ether. Orange crystals wereobtained after filtration and drying. ¹H NMR (600 MHz, CDCl₃) δ 7.49 (d,J=7.5 Hz, 4H), 7.38 (t, J=7.5 Hz, 4H), 7.28 (dd, J=12.3, 5.0 Hz, 2H),7.20 (dd, J=10.0, 7.5 Hz, 4H), 7.00-6.91 (m, 6H), 6.86 (dd, J=5.0, 3.6Hz, 2H), 6.73 (dd, J=3.6, 0.9 Hz, 2H), 6.39 (s, 2H).

Example 21 Synthesis of S0393,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(4,4′,5,5′-tetramethyl-2,2′-bithiophene)

Synthesis of 4-bromo-4′,5,5′-trimethyl-2,2′-bithiophene (27)

n-BuLi (2.5M in hexane) (10 mL, 25 mmol) was added dropwise to asolution of 4,5-dibromo-4′,5′-dimethyl-2,2′-bithiophene (3.37 g, 9.57mmol) in 100 mL of THF at −78° C. After 90 minutes upon addition, excessiodomethane (3.6 g, 25 mmol) was added dropwise by syringe, and themixture was stirred for 30 min, then warmed to RT and stirred foranother 3 hours. Solvents were evaporated and the residue was pouredinto water. The mixture was extracted with hexanes, dried over MgSO₄,and the solvent was evaporated to give off-yellow solid (2.71 g, 9.43mmol, 99% yield) of 4-bromo-4′,5,5′-trimethyl-2,2′-bithiophene. ¹H NMR(600 MHz, CDCl₃) δ 6.85 (s, 1H), 6.82-6.76 (m, 1H), 2.37 (s, 3H), 2.33(s, 3H), 2.11 (s, 3H)

Synthesis of 4,4′,5,5′-tetramethyl-2,2′-bithiophene (28)

n-BuLi (2.5M in hexane) (5 mL, 12.5 mmol) was added dropwise to asolution of 4-bromo-4′,5,5′-trimethyl-2,2′-bithiophene (2.71 g, 9.43mmol) in 100 mL of diethyl ether at −78° C. After 90 minutes uponaddition, excess iodomethane (2 g, 14 mmol) was added by syringe, andthe mixture was stirred for 30 min, then warmed to RT, and stirredovernight. Solvents were evaporated and the residue was poured intowater. The mixture was extracted with hexanes, dried over MgSO₄, and thesolvents were evaporated to give off-yellow solid (1.684 g, 7.57 mmol,80% yield) of 4,4′,5,5′-tetramethyl-2,2′-bithiophene. ¹H NMR (600 MHz,CDCl₃) δ 6.77 (d, J=15.0 Hz, 2H), 2.31 (s, 6H), 2.10 (s, 6H)

Synthesis of 3-bromo-4,4′,5,5′-tetramethyl-2,2′-bithiophene (29)

To a solution of 28 (3.618 g; 16.27 mmol) in chloroform (80.0 mL) wasadded N,N-dibromodimethylhydantoin (2.373 g; 8.30 mmol) in one portionat −10° C. The mixture was stirred for 0.5 h (TLC monitoring), pouredinto NaOH solution and extracted with DCM. Organic phase was separated,washed with water and dried over MgSO₄. The solvent was removed byrotary evaporation and trituration in methanol/DCM (10:1) afforded 29(4.23 g, 86%) as a colourless solid.

Synthesis of S039

S039 was prepared on 0.26 mmol scale (4% yield) according to protocol G.¹H NMR (400 MHz, CDCl₃) δ 6.42 (s, 2H), 2.32 (s, 6H), 2.17 (s, 6H), 2.09(s, 6H), 1.35 (d, J=4.1 Hz, 6H).

Example 22 Synthesis of S0404′,4″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(([2,2′:5′,2″-terthiophene]-5-carboxylicacid))

Synthesis of S040

A solution of 22 (0.6 mmol, 0.5 g) in dry ether (200 mL) was purged withargon and cooled to −75° C. Slowly, n-BuLi (1.27 mmol, 0.51 mL, 2.5M)was added and the reaction mixture was stirred for 1.5 h at −75° C.Carbon dioxide was bubbled through the suspension (TLC monitoring). Thetemperature was raised to 20° C. and the reaction was stirred overnight,concentrated, poured into NaOH solution (30 mL, 3 M) and was vigorouslyshaken. The ether phase was discarded and the aqueous suspension wasacidified with concentrated HCl. The dark green solid was collected byfiltration and dried in air to give crude di-acid. Flash chromatographywith chloroform/ethanol (10%) followed by chloroform/ethanol(10%)/acetic acid (1%) provided pure S040 (1.7 g, 2.25 mmol, 73% yield.¹H NMR (600 MHz, DMSO) δ 13.30 (s, 2H), 7.68 (d, J=3.8 Hz, 2H), 7.55 (d,J=5.0 Hz, 2H), 7.33 (d, J=3.8 Hz, 2H), 6.94-6.85 (m, 2H), 6.81 (d, J=3.1Hz, 2H), 6.57 (s, 2H).

Example 23 Synthesis of S042

Synthesis of 3-bromo-2,5-bis(4-(tert-butyl)phenyl)thiophene (30)

(30) was prepared on 83 mmol scale (89% yield) according to protocol C.

Synthesis of S042

S042 was prepared on 6.16 mmol scale (15% yield) according to protocolH2. ¹H NMR (400 MHz, CDCl₃) δ 7.37 (d, J=8.5 Hz, 4H), 7.30 (d, J=8.5 Hz,4H), 7.05 (d, J=8.4 Hz, 4H), 6.92 (d, J=8.4 Hz, 4H), 6.13 (s, 2H), 1.34(s, 18H), 0.91 (s, 18H).

Example 24 Synthesis of S0433-(2-(2,5-diphenylthiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-2-phenyl-5-(4-vinylphenyl)thiophene

Synthesis of 2,3-dibromo-5-(4-vinylphenyl)thiophene (101)

(101) was prepared on 19.4 mmol scale (57% yield) according to protocolD. ¹H NMR (600 MHz, CDCl₃) δ 7.44 (d, J=8.5, 2H), 7.42 (d, J=8.5, 2H),7.10 (s, 1H), 6.71 (dd, J=17.6, 10.9, 1H), 5.79 (d, J=17.6, 1H), 5.30(d, J=10.9, 1H).

Synthesis of 3-bromo-2-phenyl-5-(4-vinylphenyl)thiophene (31)

(31) was prepared on 18.8 mmol scale (97%) yield according to protocolD. ¹H NMR (600 MHz, CDCl₃) δ 7.70 (d, J=7.1, 2H), 7.55 (d, J=8.4, 2H),7.47-7.42 (m, 4H), 7.39 (t, J=7.4, 1H), 7.27 (s, 1H), 6.73 (dd, J=17.6,10.9, 1H), 5.80 (d, J=17.6, 1H), 5.30 (d, J=10.9, 1H).

Synthesis of3-(perfluorocyclopent-1-en-1-yl)-2-phenyl-5-(4-vinylphenyl)thiophene(32)

Compound 31 (6.41 g, 18.8 mmol) was dissolved in 500 mL anhydrous Et₂Oand cooled to −25° C. n-BuLi (2.5 M in hexane, 9.8 mL, 24.4 mmol) wasadded dropwise over 45 min. Lithiation was determined to be complete byTLC after the addition of approximately 7 mL. The lithiated speciesprecipitated from solution. Octafluorocyclopentene (5.18 mL, 37.6 mmol)was added and the reaction mixture stirred at −70° C. for 1.5 hoursbefore warming slowly to −20° C. over 30 min, to 0° C. for 30 minutesthen to room temperature for 1 hour. The reaction mixture was quenchedwith water and extracted with EtOAc (3×100 mL). The combined organicfractions were washed with brine, dried over MgSO₄ and concentratedunder vacuum. Purification by column chromatography afforded 32 (5.73 g,67% yield). ¹H NMR (600 MHz, CDCl₃) δ 7.59 (d, J=8.3, 2H), 7.46 (d,J=8.2, 2H), 7.45-7.35 (m, 6H), 6.74 (dd, J=17.6, 10.9, 1H), 5.81 (d,J=17.6, 1H), 5.31 (d, J=10.9, 1H).

Synthesis of S043

Compound 4 (1.61 g, 5.11 mmol) was dissolved in anhydrous Et₂O (100 mL)and cooled to −25° C. A solution of BuLi (2.2 mL, 5.44 mmol, 2.5 M inhexanes) was added dropwise over 30 minutes. Lithiation was monitored byTLC (hexanes) and determined to be complete after addition of 2.2 mL.Compound 32 (1.55 g, 3.40 mmol) was dissolved in anhydrous ether (50 mL)and added dropwise via cannula to the lithiated mixture at −40° C. Thereaction mixture stirred for 16 hours while slowly warming to roomtemperature. The reaction mixture was quenched with water and extractedwith EtOAc (3×50 mL). The combined organic fractions were washed withbrine, dried over MgSO₄ and concentrated onto silica gel. Flashchromatography yielded S043 as a white solid (1.02 g, 45% yield). ¹H NMR(400 MHz, CDCl₃) δ 7.44-7.28 (m, 9H), 7.12-7.06 (m, 6H), 7.03-6.98 (m,3H), 6.74 (dd, J=17.6, 11.0, 1H), 6.28 (s, 2H), 5.81 (d, J=17.6, 1H),5.31 (d, J=11.0, 1H).

Example 25 Synthesis of S0443,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-(trifluoromethyl)phenyl)thiophene)

Synthesis of (33)

(33) was prepared on 10 mmol scale (32% yield) according to protocol C.¹H NMR (600 MHz, CDCl₃) δ 7.83 (d, J=8.1, 2H), 7.72 (d, J=8.2, 2H), 7.69(d, J=8.8, 2H), 7.67 (d, J=8.8, 2H), 7.37 (s, 1H).

Synthesis of Compound S044

S044 was prepared according to protocol A. ¹H NMR (400 MHz, CDCl₃) δ7.65 (d, J=8.2, 4H), 7.44 (d, J=8.1, 4H), 7.38 (d, J=8.1, 4H), 7.14 (d,J=8.0, 4H), 6.39 (s, 2H).

Example 26 Synthesis of S047 and S048

Synthesis of 3′-(2-([2,2′:5′,2″-terthiophen]-3′-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-5″-bromo-2,2′:5′,2″-terthiophene(34)

S001 (7.00 g, 10.5 mmol) was dissolved in CHCl₃ (250 mL). Br₂ (1.67 g,10.47 mmol) was dissolved in 100 mL CHCl₃ and added to the S001 solutiondropwise over 3 hours. The reaction mixture was washed with water (100mL) followed by brine (2×50 mL). The solution was dried over MgSO₄ andconcentrated onto silica gel. Flash chromatography (95:5 hexanes/CHCl₃)afforded 34 (4.30 g, 55%). ¹H NMR (600 MHz, CDCl₃) δ 7.27-7.25 (m, 1H),7.19 (dd, J=5.1, 1.2, 1H), 7.16 (dd, J=5.1, 1.2, 1H), 7.07 (dd, J=3.6,1.1, 1H), 7.02 (dd, J=5.1, 3.6, 1H), 6.98 (d, J=3.8, 1H), 6.85 (dd,J=5.1, 3.6, 1H), 6.84-6.80 (m, 2H), 6.72-6.70 (m, 2H), 6.37 (s, 1H),6.30 (s, 1H).

Synthesis of S047

(4′-(2-([2,2′:5′,2″-terthiophen]-3′-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-[2,2′:5′,2″-terthiophene]-5-carboxylicacid): Compound 34 (4.30 g, 5.75 mmol) was dissolved in anhydrous Et₂O(600 mL) and cooled to −78° C. BuLi (2.4 mL, 6.0 mmol, 2.5 M solution inhexanes) was added dropwise over 30 minutes. The lithiation wasmonitored by TLC (95:5 hexanes/CHCl₃) and determined to be incomplete soanother 0.5 equivalents of n-BuLi was added. The mixture was left tostir for another 20 minutes and again monitored by TLC. A final 0.5 mLBuLi was added and the lithiation was determined to be complete. Carbondioxide gas was passed through a bubbler containing H₂SO₄ followed by aplug of Drierite and then bubbled through the reaction mixture for 16hours. The mixture was then quenched with 5% HCl (aq) and concentratedto remove Et₂O. The mixture was extracted with CHCl₃ (3×100 mL). Thecombined organic fractions were washed with brine, dried over MgSO₄ andconcentrated to dryness under vacuum. Flash chromatography (CHCl₃)yielded 1.8 g of S047. ¹H NMR (400 MHz, CDCl₃) δ 7.80 (d, J=4.0, 1H),7.30-7.22 (m, 1H), 7.23-7.13 (m, 2H), 7.11-7.05 (m, 2H), 7.05-6.98 (m,1H), 6.89-6.81 (m, 2H), 6.78-6.68 (m, 2H), 6.50 (s, 1H), 6.38 (s, 1H).

Synthesis of S048

(4-(1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)phenyl4′-(2-([2,2′:5′,2″-terthiophen]-3′-yl)-3,3,4,4,5,5-hexafluorocyclopent-en-yl)-[2,2′:5′,2″-terthiophene]-5-carboxylate):Oxalyl chloride (0.83 mL, 9.84 mmol) was added to S047 (1.40 g, 1.97mmol) in CHCl₃ (100 mL). The acid did not fully dissolve until acylchloride began to form. To this mixture was added a single drop of DMF.The reaction flask was fitted with a bubbler to monitor the amount ofgas evolved as the reaction proceeded. The reaction mixture stirred atroom temperature for 3 hours. At this time the acyl chloride formationwas determined to be complete by TLC (CHCl₃). The reaction mixture wasthen concentrated to dryness. The acyl chloride was then dissolved inanhydrous THF (120 mL). To this solution was added 6 mL Et₃N (purifiedby refluxing with Ac₂O followed by distillation and then a seconddistillation 12 days prior to use) A solution of the phenol (0.76 g,2.96 mmol) in anhydrous THF (50 mL) was transferred into the acylchloride solution over 30 minutes and stirred at room temperature for 20hours. The mixture was then concentrated to dryness and redissolved inCHCl₃ (200 mL) and washed with 5% HCl, dried over MgSO₄ and evaporatedto dryness. The crude product was purified by flash columnchromatography (2% MeOH in CHCl₃, 2 successive columns) yielding 0.77 gof S048. ¹H NMR (400 MHz, CDCl₃) δ 7.88 (d, J=4.0, 1H), 7.42-7.34 (m,4H), 7.28-7.25 (m, 1H), 7.19 (dd, J=5.1, 1.1, 2H), 7.11 (d, J=3.9, 1H),7.07 (dd, J=3.6, 1.2, 1H), 7.02 (dd, J=5.1, 3.6, 1H), 6.87-6.82 (m, 2H),6.75 (dd, J=3.6, 1.2, 1H), 6.72 (dd, J=3.6, 1.2, 1H), 6.59 (s, 2H), 6.52(s, 1H), 6.38 (s, 1H), 5.42 (s, 2H), 3.04 (s, 2H).

Example 27 Synthesis of S0493,3″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-(tert-butyl)phenyl)-2,2′-bithiophene)

Synthesis of 2,3-dibromo-5-(4-(tert-butyl)phenyl)thiophene (105)

105 was prepared on 12.3 mmol scale (44% yield) according to protocol D.¹H NMR (600 MHz, CDCl₃) δ 7.45-7.39 (m, 4H), 7.07 (s, 1H), 1.34 (s, 9H).

Synthesis of 3-bromo-5-(4-(tert-butyl)phenyl)-2,2′-bithiophene (106)

(106) was prepared on 4.2 mmol scale (79%) yield according to protocolB. ¹H NMR (400 MHz, CDCl₃) δ 7.54-7.40 (m, 5H), 7.36 (dd, J=5.1, 1.1,1H), 7.20 (s, 1H), 7.10 (dd, J=5.1, 3.7, 1H), 1.36 (s, 9H).

Synthesis of S049

S049 was prepared on 0.36 mmol scale (17.3% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.21 (dd, J=4.9, 1.4, 1H), 7.13 (d, J=8.4,2H), 7.04-6.98 (m, 2H), 6.92 (d, J=8.4, 2H), 6.08 (s, 2H), 1.04 (s,18H).

Example 28 Synthesis of S0503,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-phenylthiophene)

Synthesis of S050

S002 was prepared as described in U.S. Pat. No. 7,777,055. To thesolution of S002 (0.306 g; 0.475 mmol) in a mixture of acetic acid (10.0mL) and DCM (10.0 mL) was added bromine (0.05 mL; 0.973 mmol) as asolution in DCM (3 mL). Ammonium nitrate was added as a catalyst and themixture was heated to reflux overnight. After cooling to RT, DCM wasremoved under vacuum. The remaining acetic acid solution was poured intowater and extracted with DCM. The organic layer was separated, washedwith sodium thiosulfate solution and water, and concentrated. Flashchromatography (hexanes) afforded S050 (0.36 g; 94%). ¹H NMR (400 MHz,CDCl₃) δ 7.43 (d, J=8.4 Hz, 4H), 7.15 (d, J=8.4 Hz, 4H), 7.05-6.98 (m,6H), 6.95-6.88 (m, 4H), 6.19 (s, 2H).

Example 29 Synthesis of S0524,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-(tert-butyl)phenyl)-2,2′-bithiophene)

Synthesis of 4-bromo-5-(4-(tert-butyl)phenyl)-2,2′-bithiophene (108)

(108) was prepared on 5.5 mmol scale (100% yield) according to protocolD. ¹H NMR (400 MHz, CDCl₃) δ 7.63 (d, J=8.6, 2H), 7.47 (d, J=8.6, 2H),7.26 (dd, J=5.1, 1.1, 1H), 7.19 (dd, J=3.6, 1.1, 1H), 7.13 (s, 1H), 7.04(dd, J=5.1, 3.6, 1H), 1.37 (s, 9H).

Synthesis of S052

S052 was prepared on 0.091 mmol scale (3.3% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.40 (d, J=8.5, 4H), 7.35 (d, J=8.5, 4H),7.11 (dd, J=5.1, 1.1, 2H), 6.80 (dd, J=5.1, 3.6, 2H), 6.72 (dd, J=3.6,1.1, 2H), 6.50 (s, 2H), 1.36 (s, 18H).

Example 30 Synthesis of S0534,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methoxy-2,2′-bithiophene)

Synthesis of 3,5-dibromo-2-methoxythiophene (35)

(35) was prepared on 22.1 mmol scale (85% yield) according to protocolF1.

Synthesis of 4-bromo-5-methoxy-2,2′-bithiophene (36)

(36) was prepared on 13 mmol scale (59% yield) according to protocol B.¹H NMR (400 MHz, CDCl₃) d 7.16 (dd, J=5.1, 1.2 Hz, 1H), 7.02 (dd, J=3.6,1.2 Hz, 1H), 6.97 (dd, J=5.1, 3.6 Hz, 1H), 6.82 (s, 1H), 3.97 (s, 3H).

Synthesis of S053

S053 was prepared on 0.56 mmol scale (15% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.17 (dd, J=5.1, 1.1 Hz, 2H), 7.04 (dd,J=3.6, 1.1 Hz, 2H), 7.00-6.96 (m, J=4.8 Hz, 4H), 3.69 (s, 6H).

Example 31 Synthesis of S0543,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-methoxyphenyl)thiophene)

Synthesis of 3-bromo-2,5-bis(4-methoxyphenyl)thiophene (37)

(37) was prepared on 13 mmol scale (65% yield) according to protocol C.

Synthesis of S054

S054 was prepared on 5.82 mmol scale (41% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.32 (d, J=8.7 Hz, 4H), 6.91 (dd, J=8.7,2.4 Hz, 9H), 6.60 (d, J=8.6 Hz, 4H), 6.25 (s, 2H), 3.85 (s, 6H), 3.41(s, 6H).

Example 32 Synthesis of S0554,5-bis(2,5-diphenylthiophen-3-yl)-2-phenylthiazole

Synthesis of S055

(4) (5.93 g, 18.8 mmol) was dissolved in Et₂O (100 mL) and cooled to−30° C. BuLi (8.8 mL, 22 mmol, 2.5 M in hexanes) was added dropwise over30 minutes. After the reaction mixture stirred for an additional 30minutes, B(OBu)₃ (5.6 mL, 20.7 mmol) was added and the reaction mixturewas stirred for 1 hour while warming from −30° C. to 0° C. The coolingbath was then removed and the reaction mixture stirred for another hour.The reaction mixture was then concentrated to dryness and redissolved inTHF (60 mL). To the reaction mixture was added 20% Na₂CO₃ (aq) (60 mL),compound (19) (2 g, 6.27 mmol) and the mixture was then deoxygenated bybubbling with argon 30 minutes. To this mixture was added Pd(PPh₃)₄ (0.2g, 0.2 mmol) and the reaction mixture was heated to reflux for 16 hours.After cooling, the layers were separated and the aqueous layer wasextracted with EtOAc (2×50 mL). The combined organic fractions werewashed with brine (50 mL), dried over MgSO₄, filtered and concentratedonto silica gel. Flash chromatography (8:2 hexanes/chloroform followedby 1:1 hexanes/chloroform) afforded 3.86 g (98%). ¹H NMR (400 MHz,CDCl₃) δ 8.04-7.98 (m, 2H), 7.51-7.43 (m, 5H), 7.43-7.34 (m, 6H),7.33-7.27 (m, 2H), 7.11-6.98 (m, 10H), 6.80 (s, 1H), 6.47 (s, 1H).

Example 33 Synthesis of S0563,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-chlorophenyl)thiophene)

Synthesis of 3-bromo-2,5-bis(4-chlorophenyl)thiophene (38)

(38) was prepared on 13 mmol scale (34% yield) according to protocol C.

Synthesis of S056

S056 was prepared on 3.2 mmol scale (46% yield) according to protocol G.¹H NMR (400 MHz, CDCl₃) δ 7.43-7.31 (m, 9H), 7.15-7.04 (m, 4H), 6.92 (d,J=8.3 Hz, 4H), 6.37 (s, 2H).

Example 34 Synthesis of S0573,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-tert-butylphenyl)-5-phenylthiophene)

Synthesis of 3-bromo-2-(4-tert-butylphenyl)-5-phenylthiophene (39)

(39) was prepared on 24.1 mmol scale (81%) according to protocol D.

Synthesis of S057

S057 was prepared on 4.14 mmol scale (34% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.29 (td, J=8.5, 4.5 Hz, 8H), 7.19 (dd,J=9.3, 4.3 Hz, 2H), 7.00 (d, J=8.3 Hz, 4H), 6.86 (d, J=8.3 Hz, 4H), 6.13(s, 2H), 0.87 (s, 18H).

Example 35 Synthesis of S0593-(2-(2,5-bis(4-tert-butylphenyl)thiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-enyl)-2-phenyl-5-(4-vinylphenyl)thiophene

Synthesis of S059

Compound (30) (3.47 g; 8.11 mmol) was dissolved in anhydrous diethylether (250 mL) and cooled to −25° C. n-BuLi (3.6 mL; 8.9 mmol; 2.5 M inhexane) was added. The mixture was stirred for 10 min. Compound (32)(3.35 g; 7.37 mmol) was added as ether solution (50 mL) dropwise over 10min. The reaction mixture was allowed to warm slowly overnight, and thenquenched by addition of 10% aqueous HCl (50 mL). Organic layer wasseparated; aqueous phase was extracted with EtOAc (150 mL). Solventswere evaporated and the crude material was purified by column elutingwith hexane. Collected product was sonicated in methanol and pale yellowpowder was filtered and dried in air (3.464 g; 1.87 mmol; yield 60%). ¹HNMR (400 MHz, CDCl₃) δ 7.43-7.36 (m, 5H), 7.47-7.29 (m, 8H), 7.34 (d,J=8.3 Hz, 2H), 7.30-7.26 (m, 2H), 7.12-7.10 (m, 2H), 7.11 (dd, J=6.2,3.0 Hz, 5H), 7.09 (s, 2H), 7.01 (dd, J=6.5, 2.9 Hz, 2H), 7.01 (dd,J=6.5, 2.9 Hz, 2H), 6.92 (d, J=8.3 Hz, 2H), 6.92 (d, J=8.3 Hz, 2H), 6.72(dd, J=17.6, 10.9 Hz, 1H), 6.25 (s, 1H), 6.21 (s, 1H), 5.77 (d, J=17.6Hz, 1H), 5.28 (d, J=11.0 Hz, 1H), 1.36 (s, 9H), 0.97 (s, 9H).

Example 36 Synthesis of S0603,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)-5-(4-chlorophenyl)thiophene

Synthesis of 2,3-dibromo-5-(4-chlorophenyl)thiophene (39a)

(39a) was prepared on 15 mmol scale (38% yield) according to protocol D.

Synthesis of 3-bromo-2-(4-tert-butylphenyl)-5-(4-chlorophenyl)thiophene(40)

(40) was prepared on 22.2 mmol scale (76% yield) according to protocolD.

Synthesis of S060

S060 was prepared on 3.75 mmol scale (34% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.29 (m, 8H), 7.08 (d, J=8.3 Hz, 4H),6.91 (d, J=8.3 Hz, 4H), 6.19 (s, 2H), 0.99 (s, 18H).

Example 37 Synthesis of S0633,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-(4-tert-butylphenyl)thiophene)

Synthesis of 2,3-dibromo-5-(4-chlorophenyl)thiophene (39a)

(39a) was prepared on 15 mmol scale (38% yield) according to protocol D.

Synthesis of 3-bromo-2-(4-tert-butylphenyl)-5-(4-chlorophenyl)thiophene(40)

(40) was prepared on 22.2 mmol scale (76% yield) according to protocolD.

Synthesis of S060

S060 was prepared on 3.75 mmol scale (34% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.29 (m, 8H), 7.08 (d, J=8.3 Hz, 4H),6.91 (d, J=8.3 Hz, 4H), 6.19 (s, 2H), 0.99 (s, 18H).

Example 38 Synthesis of S064(1,1′-((4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-(tert-butyl)phenyl)thiophene-4,2-diyl))bis(4,1-phenylene))diethanone)and S065((1-(4-(5-(4-tert-butylphenyl)-4-(2-(2-(4-tert-butylphenyl)-5-phenylthiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-enyl)thiophen-2-yl)phenyl)ethanone))

Synthesis of S064+S065

A solution of S063 (0.66 g, 0.72 mmol) in ether (20 mL) was cooled to−5° C. and a solution of n-BuLi in hexane (0.75 mL, 2.5 M, 1.9 mmol) wasadded dropwise. Reaction mixture was stirred for 15 min at 0 to −10° C.Anhydrous N,N-dimethylacetamide (1 mL) was added slowly as an ethersolution (15 mL) at −5° C. and the mixture was stirred for 90 min andquenched with 10% HCl solution. Organic layer was separated, aqueouslayer was extracted with EtOAc; organic fractions pooled and solventevaporated. Flash chromatography (hexanes to 30% EtOAc/hexanes) gaveS064 in 46% yield and S065 in 22% yield. S064: ¹H NMR (600 MHz, CDCl₃) δ7.95 (d, J=8.3 Hz, 4H), 7.46 (d, J=8.3 Hz, 4H), 7.08 (d, J=8.3 Hz, 4H),6.94 (d, J=8.2 Hz, 4H), 6.34 (s, 2H), 2.62 (s, 6H), 0.95 (s, 18H). S065:¹H NMR (600 MHz, CDCl₃) δ 7.95 (d, J=8.3 Hz, 2H), 7.46 (d, J=8.3 Hz,2H), 7.40-7.33 (m, 4H), 7.30-7.27 (m, 1H), 6.34 (s, 1H), 6.21 (s, 1H),2.63 (s, 3H), 0.96 (s, 9H), 0.95 (s, 9H).

Example 39 Synthesis of S0662,2′-((4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-(tert-butyl)phenyl)thiophene-4,2-diyl))bis(4,1-phenylene))bis(2-methyl-1,3-dioxolane)

Synthesis of S066

A 50 mL flask was charged with 1 mg of p-toluenesulfonic acidmonohydrate, 25 mL of benzene, 1 g (16 mmol) of ethylene glycol, and 0.2g (0.238 mmol) of S064. The solution was brought to reflux with watercollection in Dean-Stark apparatus. After 30 hours at reflux, themixture was cooled to RT and poured into 80 mL of 10% aqueous NaOH. Thebenzene layer was washed with 25 mL of brine, dried over MgSO₄ for 10minutes, and filtered. Removal of solvent and sonication of the residuein methanol provided a pale yellow solid, which was filtered off anddried under vacuum. Yield 0.22 g (0.237 mmol; 100%). ¹H NMR (600 MHz,CD₂Cl₂) δ 7.51-7.45 (m, 4H), 7.40-7.36 (m, 4H), 7.08 (d, J=8.3 Hz, 4H),6.94 (d, J=8.3 Hz, 4H), 6.22 (s, 2H), 4.06-4.00 (m, 4H), 3.80-3.72 (m,4H), 1.63 (s, 6H), 0.90 (s, 18H).

Example 40 Synthesis of S0672,2′-((4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-(tert-butyl)phenyl)thiophene-4,2-diyl))bis(4,1-phenylene))bis(propan-2-ol)(Scheme 50)

A solution of S064 (0.64 g, 0.76 mmol) in ether (100 mL) was cooled to−5° C. and a solution of MeLi in ether (12.5 mL, 1.6 M, 20 mmol) wasadded dropwise. Reaction mixture was stirred for 15 min at −5° C., thenallowed to warm to RT, and stirred overnight. TLC indicates two spots.Another 8 equivalents of MeLi (12.5 mL) was added at RT along with2-methyltetrahydrofuran (35 mL), and the mixture was continued to stirfor 16 h and quenched with 10% HCl solution. The organic layer wasseparated and the aqueous was extracted with ethyl acetate. The solventwas removed by rotary evaporation and flash chromatography (hexanes to40% EtOAc/hexanes) afforded S067 (1.44 g, 1.65 mmol) in 66% yield. 1HNMR (400 MHz, CDCl₃) δ 7.48 (d, J=8.4 Hz, 4H), 7.35 (d, J=8.4 Hz, 4H),7.06 (d, J=8.4 Hz, 4H), 6.93 (d, J=8.3 Hz, 4H), 6.17 (s, 2H), 1.72 (s,2H), 1.60 (s, 12H), 0.92 (s, 18H).

Example 41 Synthesis of S06812,12′-((4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-(tert-butyl)phenyl)thiophene-4,2-diyl))bis(4,1-phenylene))bis(12-methyl-2,5,8,11-tetraoxatridecane)

Synthesis of 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (46)

To a solution of p-toluenesulfonyl chloride (3.17 g, 19.3 mmol) in 20 mLof pyridine was added 2-(2-(2-methoxyethoxy)ethoxy)ethanol (4 g, 21mmol), which was then stirred at 0° C. for 12 h and at RT for 2 h. Tothis suspension, water, hexanes, and ethyl acetate were added andseparated. The organic layer was neutralized with dilute hydrochloricacid and separated again. The organic layer was dried over withmagnesium sulfate and sodium bicarbonate, filtered, and concentratedunder reduced pressure to give 4.87 g, 15.3 mmol (79%) of2-(2-(2-methoxyethoxy)ethoxy)-ethyl 4-methylbenzene sulfonate as acolorless oil.

Synthesis of S068

Sodium hydride (0.24 g, 6 mmol, 60% dispersion in oil) was washed withhexanes (6 mL) and a solution of S067 (1.33 g, 1.52 mmol) in THF (25 mL)was added under argon. The reaction mixture was stirred for 1 h at RT.To the resulting suspension was added a solution of (46) (1.06 g, 3.35mmol) in anhydrous DMF (12 mL) in one portion and the mixture wasstirred for 48 h. The reaction was quenched by addition of brine (100mL) and extracted with EtOAc (3×100 mL). The organic layer was washedwith water (2×100 mL), dried over MgSO₄, filtered and evaporated todryness. Flash chromatography (hexanes/EtOAc 1:1) afforded 1.24 g (1.06mmol; 70%). ¹H NMR (400 MHz, CDCl₃) δ 7.44 (d, J=8.4 Hz, 4H), 7.36 (d,J=8.4 Hz, 4H), 7.09 (d, J=8.4 Hz, 4H), 6.96 (d, J=8.3 Hz, 4H), 6.21 (s,2H), 3.72-3.68 (m, 12H), 3.66 (t, J=5.3 Hz, 5H), 3.61-3.57 (m, 4H),3.43-3.37 (m, 10H), 1.58 (s, 12H), 0.95 (s, 18H).

Example 42 Synthesis of S0733,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5′di-tert-butyl-2,2′-bithiophene)

Synthesis of 5,5′-di-tert-butyl-2,2′-bithiophene (47)

(47) was prepared on 57 mmol scale (95% yield) according to protocol E.

Synthesis of 3-bromo-5,5′-di-tert-butyl-2,2′-bithiophene (48)

(48) was prepared on 37.7 mmol scale (66% yield) according to protocolF2.

Synthesis of S073

S073 was prepared on 0.49 mmol scale (6% yield) according to protocol G.¹H NMR (400 MHz, CDCl₃) δ 6.61-6.51 (m, 2H), 6.45-6.37 (m, 2H),6.15-6.06 (m, 2H), 1.35 (d, J=12.5 Hz, 18H), 1.26 (s, 18H).

Example 43 Synthesis of S0743,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-cyanophenyl)thiophene)

Synthesis of 4,4′-(3-bromothiophene-2,5-diyl)dibenzonitrile (49)

(49) was prepared on 46 mmol scale (78% yield) according to protocol C.

Synthesis of S074

S074 was prepared on 0.29 mmol scale (13% yield) according to protocolH3. ¹H NMR (400 MHz, DMSO) δ 7.92 (d, J=8.5 Hz, 4H), 7.78 (d, J=8.5 Hz,4H), 7.59 (d, J=8.3 Hz, 4H), 7.22 (d, J=8.3 Hz, 4H), 6.83 (s, 2H).

Example 44 Synthesis of S0791,2-bis(2-(4-n-octylphenyl)-1-benzofuran-3-yl)perfluorocyclopentene

Synthesis of 2-(4-n-octylphenyl)-1-benzofuran (50)

(50) was prepared on 20.4 mmol scale (66% yield) according to protocolD.

Synthesis of 3-bromo-2-(4-n-octylphenyl)-1-benzofuran (51)

(51) was prepared on 8.8 mmol scale (43% yield) according to protocolF3.

Synthesis of S079

S079 was prepared on 0.92 mmol scale (21% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.22 (m, 4H), 7.18-7.09 (m, 4H),7.07-6.97 (m, 6H), 6.78 (d, J=8.0 Hz, 4H), 2.37-2.23 (m, 4H), 1.49-1.39(m, 4H), 1.35-1.22 (m, 21H), 0.90 (t, J=6.8 Hz, 6H).

Example 45 Synthesis of S0833,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methoxy-2-(4-methoxyphenyl)-benzofuran

Synthesis of 5-methoxybenzofuran-2-ylboronic acid (52)

5-Methoxybenzofuran (5.3 g, 35.8 mmol) was dissolved in anhydrous THF(120 mL) and cooled to −30° C. The solution was treated with n-BuLi (18mL, 45 mmol, 2.5 M in hexanes) over 30 min, maintaining the internaltemperature at −30° C. during the addition to give a yellow solution.After 1 h at −30° C., tributyl borate (12.2 mL, 45.1 mmol) was addedover 10 min and the solution became pale yellow. The resulting solutionwas allowed to warm slowly to 14° C. over 12 h, then was quenched with 6M HCl (50 mL) and extracted with EtOAc (150 mL). The organics werewashed with water, then brine and dried over MgSO₄. After filtration,the organic solution was concentrated and the boronic acid precipitatedby the addition of hexanes. The solid was filtered and washed withhexanes to give an off-white solid (3.95 g, 48%).

Synthesis of 5-methoxy-2-(4-methoxyphenyl)benzofuran (53)

(53) was prepared on 8.8 mmol scale (56% yield) according to protocol D.

Synthesis of 3-bromo-5-methoxy-2-(4-methoxyphenyl)benzofuran (54)

(54) was prepared on 9.6 mmol scale (83% yield) according to protocolF4.

Synthesis of S083

S083 was prepared on 1.1 mmol scale (22% yield) according to protocol H3with the following exception: instead of using silica gel as thestationary phase in the flash chromatography step, basic alumina wasused. ¹H NMR (400 MHz, CDCl₃) δ 7.17 (d, J=8.9 Hz, 2H), 7.01-6.96 (m,4H), 6.75 (dd, J=8.9, 2.6 Hz, 2H), 6.54 (s, 2H), 6.48 (d, J=8.7 Hz, 4H),3.79 (d, J=4.6 Hz, 6H), 3.67 (s, 6H).

Example 46 Synthesis of S0843,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-hydroxyphenyl)thiophene)(Scheme 56)

To a solution of S054 (3.29 g, 4.3 mmol) in 150 mL of dichloromethane at0° C. was added BBr₃ (1.0 M in DCM, 26 mL, 1.5 eq.). The resultingmixture was allowed to warm to RT and stirred for 12 h. Methanol wasthen added slowly to quench the reaction at 0° C. and the mixture waspoured into water (300 mL) and extracted with EtOAc. Organic solventswere removed under vacuum. The residue was purified by sonication inchloroform and filtration. The grey solid was dried to give 2.81 g ofS084. Yield 92%. ¹H NMR (400 MHz, DMSO) δ 9.68 (s, 2H), 9.57 (s, 2H),7.21 (d, J=8.3 Hz, 4H), 6.77 (dd, J=15.5, 8.3 Hz, 8H), 6.55 (d, J=8.3Hz, 4H), 6.20 (s, 2H).

Example 47 Synthesis of S085, S086 and S087

Synthesis of 3-bromo-2-(4-methoxyphenyl)thiophene (55)

(55) was prepared on 85 mmol scale (82% yield) according to protocol D.

Synthesis of 3,5-dibromo-2-(4-methoxyphenyl)thiophene (56)

(56) was prepared on 59 mmol scale (70% yield) according to protocol F4.

Synthesis of 4-(4-bromo-5-(4-methoxyphenyl)thiophen-2-yl)benzonitrile(57)

(57) was prepared on 28.4 mmol scale (86% yield) according to protocolD.

Synthesis of S085

S085 was prepared according to protocol H3. ¹H NMR (400 MHz, CDCl₃) δ7.67 (d, J=8.5 Hz, 4H), 7.46 (d, J=8.5 Hz, 4H), 6.92 (d, J=8.7 Hz, 4H),6.59 (d, J=6.8 Hz, 4H), 6.47 (s, 2H), 3.42 (s, 6H).

Preparation of S086(4,4′-(3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-methoxyphenyl)thiophene-3,2-diyl))dibenzonitrile)

Synthesis of 2,3-dibromo-5-(4-methoxyphenyl)thiophene (58)

(58) was prepared on 26.4 mmol scale (40% yield) according to protocolD.

Synthesis of 4-(3-bromo-5-(4-methoxyphenyl)thiophen-2-yl)benzonitrile(59)

(59) was prepared on 17 mmol scale (64% yield) according to protocol D.

Synthesis of S086

S086 was prepared on 0.39 mmol scale (9.7% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.38 (d, J=8.4 Hz, 4H), 7.30 (d, J=8.8 Hz,4H), 7.09 (d, J=8.5 Hz, 4H), 6.99 (d, J=8.8 Hz, 4H), 6.23 (s, 2H), 3.87(s, 6H).

Preparation of S087

(4-(3-(2-(5-(4-cyanophenyl)-2-(4-methoxyphenyl)thiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-5-(4-methoxyphenyl)thiophen-2-yl)benzonitrile):S087 is prepared in two steps using precursors prepared as per synthesisof S085 and S085.

Synthesis of4-(5-(4-methoxyphenyl)-4-(perfluorocyclopent-1-en-1-yl)thiophen-2-yl)benzonitrile(60)

To a solution of (57) (5.0 g, 13.50 mmol) in dry THF (300 mL) was slowlyadded n-BuLi hexane solution (2.0 M, 7.43 mL, 14.85 mmol) at −50° C.under an argon atmosphere. The solution was stirred for 15 minutes at−50° C. After the addition of octafluorocyclopentene (5.44 mL, 40.5mmol), the reaction mixture was stirred for 2 h. The reaction wasquenched by the addition of methanol and warmed to RT. The solvents wereremoved by rotary evaporation and flash chromatography (10% EtOAc inhexanes) afforded a dark yellow oil (4.0 g, 61.3%).

Synthesis of S087

To a solution of (59) (2.66 g, 7.20 mmol) in dry THF (190 mL) was slowlyadded n-BuLi hexane solution (2.0 M, 3.96 mL, 7.91 mmol) at −50° C.under an argon atmosphere. The solution was stirred for 15 minutes at−50° C., compound (60) (4.0 g in 50 mL of dry THF, 8.27 mmol) was addedunder argon, and the reaction mixture stirred for a further 2 h, andstopped by quenching it with methanol. THF and ether were then removedunder vacuum. EtOAc and water were added to the reaction crude. Theproduct was extracted with EtOAc and the organic layer was dried overMgSO₄ and concentrated under vacuum. The resulting brown solid waspurified by column chromatography (Silica gel; 20% EtOAc in hexanes toprovide a brown/yellowish solid 543 mg (10.0%). This solid was dissolvedin DCM and purified again by column chromatography (aluminum oxide) andtreated first with hexanes, followed by a gradual increase in polarity(3%, 6%, 10% and 20% of EtOAc in hexanes)—the product was collected at20% EtOAc in hexanes. A final purification by preparative TLC using amixture of 20% EtOAc in hexanes was performed. ¹H NMR (400 MHz, CDCl₃) δ7.73 (d, J=8.5 Hz, 2H), 7.46 (d, J=8.5 Hz, 2H), 7.36 (d, J=8.6 Hz, 2H),7.34 (d, J=11.4 Hz, 2H), 7.10 (d, J=8.4 Hz, 2H), 6.92 (t, J=8.2 Hz, 4H),6.63 (d, J=8.7 Hz, 2H), 6.42 (s, 1H), 6.30 (s, 1H), 3.86 (s, 3H), 3.42(s, 3H).

Example 48 Synthesis of S088(E)-3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-methoxyphenyl)-5-(4-((E)-styryl)phenyl)thiophene)

Synthesis of 3,5-dibromo-2-(4-methoxyphenyl)thiophene (61)

(61) was prepared on 90.2 mmol scale (97% yield) according to protocolF4.

Synthesis of 4-(4-bromo-5-(4-methoxyphenyl)thiophen-2-yl)benzaldehyde(62): (62) was prepared on 67.2 mmol scale (74% yield) according toprotocol D.

Synthesis of (E)-3-bromo-2-(4-methoxyphenyl)-5-(4-styrylphenyl)thiophene(63)

A mixture of benzyltriphenylphosphonium bromide (23.7 g, 54.7 mmol) and(62) (17 g, 45.5 mmol) was dispersed in chloroform (300 mL) and stirredat RT under argon atmosphere for 15 min. A solution of t-BuOK (10.3 g,91 mmol) in anhydrous THF (80 mL) was added dropwise. The reactionmixture was stirred at RT for 3 h. Then water was added, followed byextraction with chloroform. The combined extracts were dried overanhydrous MgSO₄ and solvent evaporated to half of its initial volume byrotary evaporation; the resulting light yellow precipitation wasfiltered and dried (9.63 g; 47% yield).

Synthesis of S088

To a stirred THF suspension (350 mL) containing (63) (6.12 g, 13.7mmol), 7.2 mL of 2.5 M n-BuLi hexane solution (17.8 mmol) was slowlyadded at −35° C., and the solution was stirred for 15 min.Octafluorocyclopentene (0.92 mL, 6.84 mmol) was added in one portion tothe reaction mixture and stirred with gradual warming to 20° C. over 16hours. The precipitation was filtered off and filtrate was evaporatedunder vacuum. The crude product was purified by column chromatography onsilica gel (hexane/chloroform 20 to 50%) to give 0.92 g of S088 in 14.8%yield. ¹H NMR (400 MHz, CD₂Cl₂) δ 7.64-7.51 (m, 8H), 7.47-7.34 (m, 8H),7.29 (dt, J=11.4, 4.7 Hz, 2H), 7.18 (d, J=3.2 Hz, 4H), 6.99-6.91 (m,4H), 6.65-6.58 (m, 4H), 6.43 (s, 2H), 3.38 (s, 6H).

Example 49 Synthesis of S0893,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-methoxyphenyl)-5-(4-((1E,3E)-4-phenylbuta-1,3-dien-1-yl)phenyl)thiophene)

Synthesis of3-bromo-2-(4-methoxyphenyl)-5-(4-((1E,3E)-4-phenylbuta-1,3-dienyl)phenyl)thiophene(64)

10.83 g (23.6 mmol) of Cinnamyltriphenylphosphonium bromide was added to2.70 g (24.10 mmol) of t-BuOK in 100 mL THF and the resulting solutionwas stirred at RT for 30 min. The reaction mixture was cooled to 0° C.and 8 g (21.4 mmol) of the aldehyde (62) was added in 35 mL THF. Thesolution was warmed to RT and stirred for 5 hrs. The solution was pouredinto 200 mL water. The precipitated product was separated by filtrationto give 7.5 g (74% yield) of pure target molecule.

Synthesis of S089

To a stirred THF solution (400 mL) containing3-bromo-2-(4-methoxyphenyl)-5-(4-((1E,3E)-4-phenylbuta-1,3-dienyl)phenyl)thiophene(7.47 g, 15.78 mmol), 8.2 mL of 2.5 M n-BuLi hexane solution (20.5 mmol)was slowly added at −30° C., and the solution was stirred for 15 min.Octafluorocyclopentene (1.1 mL, 7.9 mmol) was added in one portion tothe reaction mixture and stirred with gradual warming to 20° C. over 12hours. The reaction mixture was quenched by addition of 10% HCl solutionand extracted with EtOAc. The organic phase was separated and theprecipitation was filtered off. The filtrate was evaporated undervacuum. The crude product was purified by column chromatography onsilica gel (hexane/chloroform 20 to 50% gradient) to give 1.14 g of S089in 15% yield. ¹H NMR (400 MHz, CD₂Cl₂) δ 7.56-7.48 (m, 8H), 7.46-7.36(m, 8H), 7.29 (t, J=7.3 Hz, 2H), 7.13-7.02 (m, 4H), 6.98 (d, J=8.7 Hz,4H), 6.83-6.71 (m, 4H), 6.64 (d, J=8.7 Hz, 4H), 6.45 (s, 2H), 3.41 (s,6H).

Example 50 Synthesis of S0904,4′-(((((4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-methoxyphenyl)thiophene-4,2-diyl))bis(4,1-phenylene))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(N,N-bis(4-chlorophenyl)aniline)

Synthesis of 4-(4-bromo-5-(4-methoxyphenyl)thiophen-2-yl)phenol (65)

(65) was prepared on 18.1 mmol scale (62% yield) according to protocol DSynthesis of 4-chloro-N-(4-chlorophenyl)-N-(4-methoxyphenyl)aniline(68): 4-methoxyaniline (66, 7.75 g, 62.9 mmol), 1-chloro-4-iodobenzene(67, 33 g, 138 mmol), phenanthroline (0.419 g, 2.33 mmol) and copper (I)chloride (0.23 g, 2.33 mmol) were added to a 250 mL rbf and toluene (60mL) was added. Potassium hydroxide (27.5 g, 491 mmol) was added, and thereaction was heated to reflux for 18 h. A grey/purple solid wasobserved, but the reaction was incomplete, so a further 50 mL of toluenewas added and the reaction reheated to reflux for a further 30 h. Aftercooling to RT, the mixture was poured into EtOAc (500 mL) and water (400mL). The aqueous layer was separated and extracted with EtOAc (250 mL).The combined organic portions were washed with water (3×500 mL), driedover MgSO₄, filtered and solvent removed by rotary evaporation to afforda purple liquid. Flash chromatography (hexanes to 5% EtOAc/hexanes)afforded 68 as a clear, light yellow, viscous oil, 10.79 g (50%).

Synthesis of 4-(bis(4-chlorophenyl)amino)phenol (69)

4-chloro-N-(4-chlorophenyl)-N-(4-methoxyphenyl)aniline (68, 10.79 g,31.3 mmol) was dissolved in anhydrous DCM (120 mL), and the BBr₃ (1.0 M,38 mL, 37.6 mmol) was added slowly over a period of −20 minutes. Thereaction mixture was allowed to stir under an Argon atmosphere for 18hours. The reaction mixture was slowly poured into water (500 mL) andstirred for 30 minutes. The purple organic layer was separated and theaqueous layer was extracted with DCM (100 mL). The combined organicswere washed with water (500 mL), dried over MgSO₄, filtered and solventremoved by rotary evaporation. Flash chromatography (15% EtOAc/hexanes)afforded 69 as a clear, light green viscous oil, 9.41 g (91%).

Synthesis of 4-(2-bromoethoxy)-N,N-bis-(4-chlorophenyl)aniline (70)

To a 250 mL rbf was added cesium carbonate (4.93 g, 15.14 mmol) andanhydrous acetonitrile (50 mL). A solution of4-(bis(4-chlorophenyl)amino)phenol (69, 2.5 g, 7.57 mmol) inacetonitrile (25 mL) was added, and an immediate light purple colour wasobserved. 1,2-dibromoethane (7.11 g, 37.9 mmol) was added and thereaction was heated to reflux for 5 days. After cooling to RT, thereaction mixture was poured into water (250 mL), mixed well andseparated. The aqueous portion was extracted with EtOAc (2×100 mL) andthe combined organics were washed with water (2×250 mL), dried overMgSO₄, filtered and solvent removed by rotary evaporation. Flashchromatography (2% EtOAc/hexanes) afforded 70 as a clear, colourless oil(1.42 g, 43%).

Synthesis of4-(2-(4-(4-bromo-5-(4-methoxyphenyl)thiophen-2-yl)phenoxy)ethoxy)-N,N-bis(4-chlorophenyl)aniline(71)

4-(2-bromoethoxy)-N,N-bis-(4-chlorophenyl)aniline (70, 1.40 g, 3.20mmol) and 4-(4-bromo-5-(4-methoxyphenyl)thiophen-2-yl)phenol (65, 1.16g, 3.20 mmol) were dissolved in acetonitrile (40 mL) and the cesiumcarbonate (2.09 g, 6.41 mmol) was added. The reaction mixture was heatedto reflux for 20 hours. After cooling to RT, the reaction mixture waspoured into DCM (100 mL) and water (150 mL). The mixture was mixed welland the aqueous portion extracted with DCM (2×100 mL). The combinedorganics were washed with water (2×150 mL), dried over MgSO₄, filteredand solvent removed by rotary evaporation. The resulting off-white solidwas sonicated in MeOH (100 mL), filtered and air dried to afford anoff-white powder which still contained some minor impurities by TLC.This material was allowed to stir in refluxing EtOH (150 mL) for 15minutes, cooled slightly, filtered and air dried to afford 71 as anoff-white powder (1.60 g, 70%).

Synthesis of S090

S090 was prepared on 0.021 mmol scale (2% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.32 (d, J=8.7 Hz, 4H), 7.18 (d, J=8.9 Hz,8H), 7.05 (d, J=8.9 Hz, 4H), 6.98-6.90 (m, 20H), 6.60 (d, J=8.7 Hz, 4H),6.26 (s, 2H), 4.35 (m, 8H), 3.43 (s, 6H).

Example 51 Synthesis of S091, S092, S094 and S095

S084 (1 eq) and cesium carbonate (10 eq) were dissolved in anhydrous DMF(120 ml) and the alkylbromide (R_(z)—Br) added (20 eq) (Rz=ethyl forS091; isopropyl for S092; isopentyl for S094; or neopentyl for S095).The reaction mixture was heated to 90° C. and stirred for 18-36 hours.Completion was verified by TLC—if necessary a further 12-16 eq of theR—Br was added, with continued heating and stirring. After cooling toRT, the reaction mixture was poured into water and extracted with DCM(S091, S094) or EtOAc (S092, S095). Combined organics were washed withwater, dried over MgSO₄, filtered and solvent removed by vacuum.

S091(3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-ethoxyphenyl)thiophene)):Flash chromatography (10% EtOAc/hexanes) afforded a yellow solid, whichwas sonicated in MeOH (100 mL), filtered and air dried (1.58 g). Aportion of this solid was purified by preparative TLC (25% DCM inhexanes) to afford 127 mg of S091. ¹H NMR (400 MHz, CDCl₃) δ 7.30 (d,J=8.8 Hz, 4H), 6.89 (d, J=7.5 Hz, 8H), 6.57 (d, J=8.7 Hz, 4H), 6.24 (s,2H), 4.07 (q, J=7.0 Hz, 4H), 3.51 (m, 4H), 1.45 (t, J=7.0 Hz, 6H), 1.27(t, J=6.9 Hz, 6H).

S092(3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-isopropoxyphenyl)thiophene)):Flash chromatography (10% EtOAc/hexanes) afforded a green/yellow solidwhich was sonicated in MeOH (30 mL), filtered and air dried to afford ayellow solid, 0.80 g. A portion of this solid was purified bypreparative TLC (25% DCM in hexanes) to afford 145 mg of S092. ¹H NMR(400 MHz, CDCl₃) δ 7.29 (d, J=8.7 Hz, 4H), 6.87 (d, J=8.7 Hz, 4H), 6.87(d, J=8.7 Hz, 4H), 6.58 (d, J=8.7 Hz, 4H), 6.22 (s, 2H), 4.57 (sept,J=6.1 Hz, 2H), 4.11 (sept, J=6.0 Hz, 2H), 1.37 (d, J=6.1 Hz, 12H), 1.18(d, J=6.0 Hz, 12H).

S094(3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-(isopentyloxy)phenyl)thiophene)):The resulting dark green liquid was dried on the high vacuum pump toremove the residual DMF. To the dark green oil was added MeOH (50 mL)and after standing for 2 hours, a dark green material solidified. Thesolid was filtered off, ground in a mortar and pestle, washed with MeOH(50 mL), filtered and air-dried to afford a green powdery solid. Aportion of this solid was purified by preparative TLC (25% DCM inhexanes) to afford 100 mg of S094. ¹H NMR (400 MHz, CDCl₃) δ 7.30 (d,J=8.7 Hz, 4H), 6.90 (d, J=8.7 Hz, 4H), 6.87 (d, J=8.8 Hz, 4H), 6.58 (d,J=8.7 Hz, 4H), 6.24 (s, 2H), 4.00 (t, J=6.7 Hz, 4H), 3.48 (s, 4H), 1.86(sept, J=6.7 Hz, 2H), 1.71 (m, 6H), 0.99 (d, J=6.6 Hz, 12H), 0.92 (d,J=6.6 Hz, 12H).

S095(3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(4-(neopentyloxy)phenyl)thiophene)):A portion of this material was purified by preparative TLC (25% DCM inhexanes) to afford 60 mg of S095. ¹H NMR (400 MHz, CDCl₃) δ 7.30 (d,J=8.7 Hz, 4H), 6.90 (d, J=8.6 Hz, 4H), 6.88 (d, J=8.7 Hz, 4H), 6.59 (d,J=8.7 Hz, 4H), 6.21 (s, 2H), 5.30 (s, 3H), 3.60 (s, 4H), 1.07 (s, 18H),0.93 (s, 18H).

Example 52 Synthesis of S0963,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(3-methoxyphenyl)thiophene)

Synthesis of 3-bromo-2,5-bis(3-methoxyphenyl)thiophene (72)

(72) was prepared on 55 mmol scale (74%) according to protocol C.

Synthesis of S096: S096 was prepared on 3.53 mmol scale (53% yield)according to protocol H3. ¹H NMR (400 MHz, CDCl₃) δ 7.29 (t, J=8.0 Hz,2H), 7.05 (d, J=14.8 Hz, 2H), 7.01 (d, J=7.1 Hz, 2H), 6.95-6.91 (m, 2H),6.85 (dd, J=8.2, 2.3 Hz, 2H), 6.60 (dd, J=8.4, 2.1 Hz, 4H), 6.53-6.49(m, 2H), 6.37 (s, 2H), 3.88 (s, 6H), 3.47 (s, 6H).

Example 53 Synthesis of S0973,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2,5-bis(3,5-dimethoxyphenyl)thiophene)

Synthesis of 3-bromo-2,5-bis(3,5-dimethoxyphenyl)thiophene (73)

(73) was prepared on 29 mmol scale (78%) yield according to protocol C.

Synthesis of S097

S097 was prepared on 3.96 mmol scale (69% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 6.58 (d, J=2.2 Hz, 4H), 6.45 (s, 2H), 6.42(t, J=2.2 Hz, 2H), 6.14 (m, 6H), 3.87 (s, 12H), 3.51 (s, 12H).

Example 54 Synthesis of S0984,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′tert-butyl-5-(4-methoxyphenyl)-2,2′-bithiophene)

Synthesis of 4-bromo-5-(4-methoxyphenyl)-2,2′-bithiophene (74)

(74) was prepared on 93.9 mmol scale (93% yield) according to protocolB.

Synthesis of 4-bromo-5′-tert-butyl-5-(4-methoxyphenyl)-2,2′-bithiophene(75): (75) was prepared according to protocol E.

Synthesis of S098

S098 was prepared on 15.5 mmol scale (35% yield) according to protocolH1. ¹H NMR (400 MHz, CD₂Cl₂) δ 6.93-6.89 (m, 4H), 6.87 (d, J=3.7 Hz,2H), 6.76 (d, J=3.7 Hz, 2H), 6.68-6.63 (m, 4H), 6.14 (s, 2H), 3.48 (s,6H), 1.41 (s, 18H).

Example 55 Synthesis of S103(3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-(4-methoxyphenyl)thiophene))and S116(4-(4-(2-(5-(4-bromophenyl)-2-(4-methoxyphenyl)thiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl)-5-(4-methoxyphenyl)thiophen-2-yl)-N,N-bis(4-chlorophenyl)aniline)

Synthesis of 3-bromo-5-(4-bromophenyl)-2-(4-methoxyphenyl)thiophene (76)

(76) was prepared on 24.6 mmol scale (86% yield) according to protocolD.

Synthesis of S103

S103 was prepared on 0.58 mmol scale (4.7% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.50 (d, J=8.5 Hz, 4H), 7.26-7.22 (d,J=8.5 Hz, 4H), 6.90 (d, J=8.7 Hz, 4H), 6.59 (d, J=8.7 Hz, 4H), 6.35 (s,2H), 3.42 (s, 6H).

Synthesis of bis(4-chlorophenyl)amine (77)

Under air, a 500-mL rbf was charged with (4-chlorophenyl)boronic acid(15.0 g, 96.0 mmol, 1 eq.), NH₂OH.HCl (8.0 g, 115 mmol, 1.2 eq.), CuBr(2.75 g, 19.18 mmol, 0.2 eq.), K₂CO₃ (19.89 g, 144.0 mmol, 1.5 eq.), andCH₃CN (320 mL). The reaction mixture was stirred at 70° C. for 24 h. Thecompletion of the reaction was monitored by TLC. The solvent wasevaporated under reduced pressure and the residue was purified by flashcolumn chromatography on a silica gel using 10%-20% EtOAc in hexanes togive the product as brown oil that solidifies when dried under vacuum.

Synthesis of S116

In a one-neck 100-mL RBF containing S103 (350 mg, 0.406 mmol, 1 eq.),213 mg of bis(4-chlorophenyl)amine (0.893 mmol, 2.2 eq.) were addedfollowed by 100 mg of potassium tert-butoxide (0.893 mmol, 2.2 eq.).Xylene (20 mL) was then added and the mixture was deoxygenated for onehour using argon. Pd(dppf)Cl₂ (6.55 mg, 9.33 mol, 0.023 eq.) was thenadded to the reaction mixture and the RBF was connected to a condenser,where the reaction was heated to 130° C. for 48 hours. The heat wasstopped and the reaction mixture was allowed to cool down to RT. Themixture was vacuum filtered through silica to remove the insolubleinorganics/catalyst and washed with DCM. The solvents (Xylene and DCM)were then removed under vacuum to provide a yellow oil. The crude wasdeposited on silica then purified by chromatography column using amixture of 5% DCM in hexanes. The polarity of the solvent was thenincreased gradually (7.5%, 10%, 12.5%, 18.75% of DCM in hexanes)according to the progress of the purification. The product was isolatedas yellow solid in 6.03% yield (˜25 mg). ¹H NMR (400 MHz, CDCl₃) δ 7.50(d, J=8.5 Hz, 2H), 7.24 (s, 4H), 7.02 (d, J=8.6 Hz, 5H), 6.91 (dd,J=8.5, 7.0 Hz, 5H), 6.61 (dd, J=17.5, 8.7 Hz, 4H), 6.35 (s, 1H), 6.26(s, 1H), 3.51 (s, 3H), 3.42 (s, 3H).

Example 56 Synthesis of S104 and S105

Synthesis of S105(4,4′-(4,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-(tert-butyl)-[2,2′-bithiophene]-5,4-diyl))diphenol)

To a solution of S098 (1.36 g, 1.64 mmol) in 100 mL of CH₂Cl₂ at RT wasadded BBr₃ (1.0 M, 10 mL, 3 eq.). The resulting mixture was stirred for12 h. MeOH was then added slowly to quench the reaction and the mixturewas poured into water (300 mL) and extracted with EtOAc. Organicsolvents were removed under vacuum. The residue was purified by flashchromatography (hexanes—5 to 20% EtOAc gradient). The yellow solid wasobtained and dried in vacuum to give 0.97 g of S105. Yield 74%. ¹H NMR(400 MHz, CDCl₃) δ 6.88-6.81 (m, 6H), 6.73 (d, J=3.7 Hz, 2H), 6.65-6.57(m, 4H), 6.21-6.11 (m, 2H), 4.84-4.62 (m, 2H), 1.41 (d, J=6.1 Hz, 18H).

Synthesis of S104(4,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-(tert-butyl)-5-(4-(2-methoxyethoxy)phenyl)-2,2′-bithiophene))

To a solution of S105 (0.9 g, 1.12 mmol) in 100 mL of acetonitrile at RTwas added potassium carbonate (1.56 g, 11.2 mmol). The resulting mixturewas stirred for 0.5 h and 2-bromoethyl methyl ether (1.55 g, 11.2 mmol)was added. The reaction mixture was heated to reflux and stirred for 9h. After completion, the mixture was poured into water (300 mL) andextracted with EtOAc. Organic solvents were removed under vacuum. Theresidue was purified by flash chromatography (hexanes—20% EtOAc). Theyellow solid was obtained, sonicated in ether/methanol (10:1) and driedin vacuum to give 0.79 g (77%) of S104. ¹H NMR (400 MHz, CDCl₃) δ 6.87(d, J=8.7 Hz, 4H), 6.83 (d, J=3.6 Hz, 2H), 6.73-6.71 (m, 2H), 6.68 (t,J=7.7 Hz, 4H), 6.13 (s, 2H), 3.73 (d, J=4.4 Hz, 4H), 3.62 (dd, J=9.0,4.3 Hz, 4H), 3.42 (d, J=7.2 Hz, 6H), 1.40 (d, J=4.7 Hz, 18H).

Example 57 Synthesis of S1084,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-(tert-butyl)-5-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-2″,2″′-bithiophene

Synthesis of S108

Potassium carbonate (25 g, 180 mmol, 3 eq.) was added to a suspension ofS105 (48.1 g, 60 mmol, 1 eq.) and 2-(2-(2-methoxyethoxy)ethoxy)ethyl4-methylbenzenesulfonate (46) (38.2 g, 120 mmol, 2 eq.) in anhydrousacetonitrile (800 mL) under argon and the mixture was stirred overnightat reflux. The reaction was cooled and all solids were filtered off. Thefiltrate was concentrated and flash chromatography (CombiFlash, 20%EtOAC/hexanes to 60% EtOAc/hexanes) afforded S108 (44 g; 67%) as a thickdark blue oil. ¹H NMR (500 MHz, CDCl₃) δ 6.86 (d, J=8.7 Hz, 4H), 6.82(d, J=3.6 Hz, 2H), 6.71 (d, J=3.6 Hz, 2H), 6.67 (d, J=8.7 Hz, 4H), 6.12(s, 2H), 3.72 (m, 12H), 3.64 (m, 8H), 3.55 (m, 4H), 3.38 (s, 6H), 1.40(s, 18H).

Example 58 Synthesis of S106, S128 and S170

Synthesis of S170

S1704,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-tert-butyl-5-(thiophenyl)-2,2′-bithiophene)was prepared on 17 mmol scale (78% yield) according to protocol E.

Synthesis of S106(3,3′-(3′,3″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5″-(tert-butyl)-[2,2′:5′,2″-terthiophene]-5,3′-diyl))bis(pentan-3-ol))

To a solution of S170 (6 g, 7.68 mmol) in THF (250 mL) at −35° C. wasadded n-BuLi (2.5 M in hexanes, 10 mL; 25 mmol). The mixture was stirredfor 20 min. and the temperature reached −10° C. Di-ethyl ketone (2 g, 23mmol) in THF (25 mL) was added to the reaction which was allowed to warmto RT and quenched with 10% HCl, extracted with ether/EtOAc. Organicsolution was dried and evaporated. Column purification provided targetdi-alcohol (6.18 g, 6.48 mmol) in 84% yield as a slowly solidifyingliquid. ¹H NMR (400 MHz, CDCl₃) δ 6.90 (d, J=3.7 Hz, 2H), 6.76-6.72 (m,2H), 6.60 (d, J=3.7 Hz, 2H), 6.56 (d, J=3.7 Hz, 2H), 6.44 (s, 2H), 1.72(dd, J=14.1, 7.4 Hz, 4H), 1.62-1.55 (m, 4H+2H OH), 1.40 (s, 18H), 0.75(t, J=7.4 Hz, 12H)

Synthesis of S128(13,13′-(3′,3″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5″-(tert-butyl)-[2,2′:5′,2″-terthiophene]-5,3′-diyl))bis(13-ethyl-3,6,9,12-tetraoxapentadecane)):NaH (0.1 g, 2.5 mmol, 60% dispersion in oil) was added to a solution ofS106 (0.95 g, 0.997 mmol) in THF (50 mL) under argon. The reactionmixture was stirred for 0.25 h at RT. To resulting suspension was addeda solution of (103) (0.73 g, 2.5 mmol) in anhydrous THF (10 mL) in oneportion and the mixture was stirred for 1 h at RT and then refluxed for2 h. Reaction was quenched by addition of saturated brine (100 mL) andextracted with ether. The organic layer was washed with water, driedover MgSO₄, filtered and evaporated to dryness. The residue was purifiedby column chromatography using a hexane/EtOAc gradient as the eluent toobtain S128 (0.446 g, 0.35 mmol; 35%) as thick dark green oil. ¹H NMR(500 MHz, CDCl₃) δ 6.84 (t, J=4.3 Hz, 2H), 6.70 (d, J=3.6 Hz, 2H), 6.56(d, J=3.6 Hz, 2H), 6.53-6.50 (m, 2H), 6.46 (s, 2H), 3.64 (dq, J=9.6, 3.7Hz, 16H), 3.57 (qd, J=8.2, 3.4 Hz, 14H), 3.53-3.45 (m, 9H), 3.26 (dd,J=11.9, 6.8 Hz, 5H), 1.82-1.68 (m, 12H), 1.40 (d, J=5.9 Hz, 21H),1.23-1.16 (m, 14H), 0.79-0.69 (m, 16H).

Example 59 Synthesis of S1094,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-(tert-butyl)-5-(4-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)phenyl)-2,2′-bithiophene)

Synthesis of 2-(2-(2-ethoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate(103)

In a 3-neck, 2 L rbf, NaOH (135 g, 3.37 mol) was added slowly to water(1 L). After the addition was complete, the solution was cooled to roomtemperature and DCM (2 L) added, followed by triethylene glycolmonoethyl ether (500 g, 2.81 mol). p-Toluenesulfonyl chloride (535 g,2.81 mol) was added portion-wise over a period of 10 minutes, and themixture refluxed for 2 hours. After cooling to room temperature, thereaction mixture was poured into water (2 L), mixed well and separated.The organic phase was washed with water (2×2 L), dried over MgSO₄,filtered and solvent removed by rotary evaporation. The resulting clear,colourless oil was stirred at room temperature with a 10% aqueous NaOHsolution (1 L) to hydrolyze unreacted p-toluenesulfonyl chloride. After18 hours, the material was poured into water (1 L), extracted withchloroform (500 mL) and separated. The organic portion was washed withwater (2 L), 10% HCl (2 L) and water (2 L). The material was dried overanhydrous MgSO₄, filtered and solvent removed by rotavap to afford (103)as a clear, colourless oil (595 g, 64%).

Synthesis of S109

S105 (70.0 g, 80 mmol), potassium carbonate (44.2 g, 320 mmol) andpotassium iodide (2.7 g, 16.0 mmol) in acetonitrile (1.2 L) was combinedwith (103) (55.8 g, 168 mmol) and the reaction heated to reflux for 16hours. After cooling to RT, the material was filtered through a pad ofcelite, the filtrate washed with EtOAc (500 mL) and the combinedorganics were concentrated to dryness by rotary evaporation. The driedmaterial was redissolved in DCM (500 mL) and dry-loaded onto silica gel,and purified by flash chromatography (Combi-flash; 15% hexanes to 40%EtOAc/hexanes) to afford a dark green oil 70.0 g (78%). ¹H NMR (500 MHz,CDCl₃) δ 6.86 (d, J=8.6 Hz, 4H), 6.82 (d, J=3.6 Hz, 2H), 6.71 (d, J=3.6Hz, 2H), 6.67 (d, J=8.6 Hz, 4H), 6.12 (s, 2H), 3.77-3.64 (m, 20H),3.61-3.57 (m, 4H), 3.52 (q, J=7.0 Hz, 4H), 1.40 (s, 18H), 1.21 (t, J=7.0Hz, 6H)

Example 60 Synthesis of S1102,2′-(4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-methoxyphenyl)thiophene-4,2-diyl))bis(benzo[b]thiophene)

Synthesis of2-(4-bromo-5-(4-methoxyphenyl)thiophen-2-yl)benzo[b]thiophene (79): (79)was prepared from (61) on 24.2 mmol scale (56% yield) according toprotocol D.

Synthesis of S110

S110 was prepared on 2.45 mmol scale (39% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.80 (d, J=7.7 Hz, 2H), 7.74 (d, J=7.1 Hz,2H), 7.39-7.30 (m, 4H), 7.27 (s, 2H), 6.94 (d, J=8.7 Hz, 4H), 6.65 (d,J=8.7 Hz, 4H), 6.35 (s, 2H), 3.34 (s, 6H).

Example 61 Synthesis of 613,3′-(4,4′-(4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-tert-butyl-2,2′-bithiophene-5,4-diyl))bis(4,1-phenylene)bis(oxy))dipropan-1-ol

To a solution of S105 (2 g, 2.5 mmol) in 100 mL of acetone at RT wasadded potassium carbonate (1.56 g, 11.2 mmol) and 18-crown-6 (6.6 g, 25mmol). The resulting mixture was stirred for 0.5 h and 3-bromopropanol(1.4 g, 10 mmol) was added. The reaction mixture was heated to refluxand stirred for 9 h. After completion the mixture was poured into water(300 mL) and extracted with hexanes. Organic solvents were removed undervacuum. The residue was purified by flash chromatography (hexanes—40%EtOAc). Two dark green oils were obtained and dried in vacuum. The topone solidified by addition of small amount of chloroform and wassonicated in hexanes/ether mixture (5:1). The light yellow solid wasthen filtered and dried in air to give 1.46 g of S11. Yield 41%. ¹H NMR(400 MHz, CDCl₃) δ 6.90-6.86 (m, 4H), 6.83 (d, J=3.6 Hz, 2H), 6.73 (d,J=3.6 Hz, 2H), 6.69-6.65 (m, 4H), 6.14 (s, 2H), 3.83-3.75 (m, 8H), 1.93(p, J=5.9 Hz, 4H), 1.41 (s, 17H).

Example 62 Synthesis of S1124,4′-((4,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-(tert-butyl)-[2,2′-bithiophene]-5,4-diyl))bis(4,1-phenylene))dimorpholine

Synthesis of 4,5-dibromo-2,2′-bithiophene (80)

(80) was prepared on 20.3 mmol scale (53% yield) according to protocolB. ¹H NMR (400 MHz, CDCl₃) δ 7.27 (dd, J=5.5, 1.5 Hz, 1H), 7.13 (dd,J=3.6, 1.1 Hz, 1H), 7.02 (dd, J=5.1, 3.6 Hz, 1H), 6.97 (s, 1H).

Synthesis of 4-(4-(4-bromo-[2,2′-bithiophen]-5-yl)phenyl)morpholine (82)

(82) was prepared on 25.3 mmol scale (62% yield) according to protocolD. ¹H NMR (400 MHz, CDCl₃) δ 7.60 (d, J=9.0 Hz, 2H), 7.25 (dd, J=5.1,1.1 Hz, 1H), 7.17 (dd, J=3.6, 1.1 Hz, 1H), 7.10 (s, 1H), 7.03 (dd,J=5.1, 3.6 Hz, 1H), 6.95 (d, J=8.9 Hz, 2H), 3.93-3.85 (m, 4H), 3.27-3.20(m, 4H).

Synthesis of4-(4-(4-bromo-5′-(tert-butyl)-[2,2′-bithiophen]-5-yl)phenyl) morpholine(83)

(83) was prepared on 23 mmol scale (79% yield) according to protocol E.¹H NMR (400 MHz, CDCl₃) δ 7.59 (d, J=8.9 Hz, 2H), 7.02 (s, 1H), 6.97 (d,J=3.6 Hz, 1H), 6.94 (d, J=8.9 Hz, 2H), 6.74 (d, J=3.7 Hz, 1H), 3.90-3.85(m, 4H), 3.25-3.21 (m, 4H), 1.40 (s, 9H).

Synthesis of S112

S112 was prepared on 1.38 mmol scale (13% yield) according to protocolG. ¹H NMR (400 MHz, CDCl₃) δ 6.86 (d, J=8.7 Hz, 2H), 6.84 (d, J=3.6 Hz,1H), 6.72 (d, J=3.6 Hz, 1H), 6.62 (d, J=8.7 Hz, 2H), 6.12 (s, 1H),3.77-3.70 (m, 4H), 2.88-2.83 (m, 4H), 1.41 (s, 9H).

Example 63 Synthesis of S113 and S11

Synthesis of carboxylic acid chloride terminated poly(dimethylsiloxane)(84)

Carboxylic acid terminated poly(dimethylsiloxane) (15 g, ca. 10 mmol)was dissolved in dry DCM (100 mL) under nitrogen and a small drop of DMFwas added. To the mixture was added oxalyl chloride (6 mL) in oneportion. The mixture was stirred at RT for no more than 30 min. Thesolvent and excess reagent were removed under vacuum and residual tracesof oxalyl chloride were removed with the aid of evaporation of1,2-dichloroethane. The acid chloride product (84) was used immediately.

Syntheses of S113 and S115

S111 (4.1 g, 4.47 mmol) was dissolved in dry DCM (150 mL) followed bythe addition of triethylamine (1.2 g, 1.6 mL, 11.7 mmol), under argon.Acid chloride end-functionalized PDMS (84) was then added dropwise in1,2-dichloroethane (10 mmol) and the mixture was left to stir at RTovernight. The solvent was then removed under vacuum, the residuere-dissolved in diethyl ether-hexane (1:1) and the mixture filteredthrough a plug of silica gel. The solvent was removed and the remainingoily residue was purified by column chromatography (silica gel,hexanes:EtOAc 8:1) to give the pure PDMS conjugate as a viscous oil:fraction 1 (S115)-17 g; fraction 2 (S113)-1.4 g. S113: ¹H NMR (400 MHz,CDCl₃) δ 6.90-6.85 (m, 4H), 6.82 (d, J=3.6 Hz, 2H), 6.72 (d, J=3.6 Hz,2H), 6.68-6.62 (m, 4H), 6.13 (s, 2H), 4.20 (t, J=6.4 Hz, 4H), 3.71 (t,J=5.9 Hz, 4H), 2.30 (t, J=7.5 Hz, 4H), 2.04-1.94 (m, 5H), 1.68-1.51 (m,10H), 1.40 (s, 18H), 1.31-1.19 (m, 30H), 0.91-0.84 (m, 7H), 0.07 (d,J=3.5 Hz, 25H).

Example 64 Synthesis of S118

Synthesis of S118

In a 100 mL rbf equipped with a stirbar, S105 (0.99 g, 1.24 mmol) andimidazole (0.37 g, 5.44 mmol) were dissolved in DCM (50 mL).Tris(OTMS)chlorosilane (1.7 mL) was added and an immediate whiteprecipitate was observed. The reaction mixture was allowed to stir at RTfor 10 minutes, then poured into water (200 mL), mixed well andseparated. The aqueous phase was extracted with DCM (50 mL) and thecombined organics were washed with water (250 mL), dried over MgSO₄,filtered and solvent removed by rotary evaporation. The resulting oilwas sonicated in MeOH (50 mL) until a fine yellow powder precipitated,which was filtered and air-dried, 1.20 g (70%) ¹H NMR (400 MHz, CDCl₃) δ6.86-6.81 (m, 6H), 6.75-6.69 (m, 6H), 6.14 (s, 2H), 1.40 (s, 18H), 0.11(s, 54H).

Example 65 Synthesis of S119 and S124

Bromination of S170

To the solution of S170 (1.06 g; 1.357 mmol) in the mixture of aceticacid (30.0 mL) and DCM (30.0 mL) was added at stirring bromine (0.434 g;2.71 mmol) as a solution in DCM (20 mL). The mixture was stirred at RTfor 20 min (TLC). DCM was evaporated The product which started toprecipitate from acetic acid was poured into water and filtered off,washed with water and dried in air to give 1.26 g (1.34 mmol; 99% yield)of non-separable mixture of two compounds (85) and (86). The mixture wasused in the next step.

Synthesis of S119+S124

To the solution of the mixture from bromination step (2.75 g, 2.93 mmol)in ether (150 mL) was added at stirring n-BuLi (2.58 mL; 6.45 mmol) as asolution in hexane at −74° C. The mixture was stirred for 20 min (TLC).Dry ice was rinsed with ether and added to the cold reaction which wasallowed to warm to RT and quenched with 10% HCl, extracted withether/EtOAc. Organic solution was dried and evaporated. Columnpurification provided target S119 (0.75 g, 0.86 mmol) in 46% yield. S124was isolated in 35% yield (0.6 g, 0.66 mmol). S119: ¹H NMR (400 MHz,DMSO) δ 13.17 (s, 2H), 7.43 (d, J=3.7 Hz, 2H), 7.06 (d, J=3.7 Hz, 2H),6.85 (d, J=3.7 Hz, 2H), 6.82 (d, J=3.7 Hz, 2H), 6.40 (s, 2H), 1.38 (s,18H). S124: ¹H NMR (400 MHz, DMSO) δ 13.14 (s, 3H), 7.48 (d, J=3.8 Hz,1H), 7.43 (d, J=3.8 Hz, 1H), 7.19-7.13 (m, 1H), 7.05 (d, J=3.7 Hz, 1H),6.83 (dd, J=6.0, 3.8 Hz, 3H), 6.73 (s, 1H), 6.38 (s, 1H), 1.38 (d, J=3.8Hz, 9H), 1.37 (s, 9H).

Example 66 Synthesis of S1353′,3″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-bis(trimethylsilyl)-2,2′:5′,2″-terthiophene)(Scheme 76)

Lithium diisopropylamide (LDA) was made by addition of BuLi (3.21 mL,8.03 mmol) to a solution of diisopropylamine (1.158 mL, 8.21 mmol) inanhydrous THF (8 mL) at 0° C. and the solution stirred at thistemperature for 30 min. The LDA solution was then added to a solution ofS001 (1.22 g, 1.824 mmol) in THF (12 mL) at 0° C. The reaction mixturewas stirred at 0° C. for 30 min then cooled to −78° C. andchlorotrimethylsilane (1.389 mL, 10.94 mmol) added. The reaction mixturewas stirred with warming to RT over 2 h and stirred at RT for 18 h. Thereaction was quenched by addition of water (10 mL). Organics wereextracted with diethyl ether (2×30 mL), washed with brine (10 mL), driedover MgSO₄, filtered and concentrated under reduced pressure. The crudeproduct was purified by column chromatography on silica gel eluting withhexanes to yield the title compound as a yellow solid (1.0 g, 57%). ¹HNMR (400 MHz, CDCl₃) δ 7.11 (d, J=3.4 Hz, 1H), 7.09 (d, J=3.4 Hz, 1H),6.86 (d, J=3.4 Hz, 1H), 6.70 (d, J=3.4 Hz, 1H), 6.37 (s, 1H), 0.34 (s,9H), 0.15 (s, 9H).

Example 67 Synthesis of S1373,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(5-methylthiophen-2-yl)benzofuran)

Synthesis of 2,3-dibromobenzofuran (87)

To a stirred DCM solution (200 mL) containing benzofuran (24 g, 203mmol) and potassium acetate (40 g, 408 mmol) 64.9 g of bromine (406mmol) was slowly added at 20° C. as a solution in DCM (100 mL). Thereaction mixture was stirred overnight at RT, poured into sodiumthiosulfate solution and extracted with DCM. The organic layer was driedover anhydrous MgSO₄, and the solution was evaporated. CombiFlashchromatography (hexanes) gave 33.6 g of the target product in 60%isolated yield.

Synthesis of 3-bromo-2-(5-methylthiophen-2-yl)benzofuran (88)

(88) was prepared on 41.8 mmol scale (96% yield) according to protocolB.

Synthesis of S137

S137 was prepared on 4.6 mmol scale (33% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.28 (m, 4H), 7.24-7.18 (m, 2H), 7.11(dd, J=11.2, 4.2 Hz, 2H), 6.77 (d, J=3.6 Hz, 2H), 6.25 (d, J=3.4 Hz,2H), 2.17 (s, 6H).

Example 68 Synthesis of S138

3.43 g of S001 (0.75 mmol) in THF (100 mL) at −20° C. was added asolution of n-BuLi (9.4 mL, 23.3 mmol. 4.5 equiv) and stirred at −20° C.for 10 min, followed by addition of (135) (6.6 g, 23.3 mmol) in THF (50mL). The reaction mixture was stirred for 1 h, warmed to roomtemperature and quenched by addition of water (30 mL). Organics wereextracted with ether (2×100 mL), washed with brine (100 mL) andconcentrated under reduced pressure. Flash chromatography (hexanes/ethylacetate) afforded S138 (1.2 g, 14%). ¹H NMR (400 MHz, CDCl₃) δ 7.15-7.12(m, 2H), 7.12-7.09 (m, 2H), 6.88 (d, J=3.4 Hz, 2H), 6.70 (d, J=3.4 Hz,2H), 6.40 (s, 2H), 3.38-3.28 (m, 60H), 1.69-1.62 (m, 12H), 1.56 (m,12H), 0.91-0.82 (m, 12H), 0.75-0.68 (m, 12H).

Example 69 Synthesis of S1395,5′-(((4,4″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-(tert-butyl)-[2″,2′″-bithiophene]-5″,4-diyl))bis(4,phenylene))bis(oxy))dipentanenitrile

Synthesis of S139

In a 500-mL 3-neck rbf, 10 g of the S105 (12.49 mmol, 1 eq.) and 415 mgof potassium iodide (2.497 mmol, 0.2 eq.) were dissolved in 250 mL ofacetonitrile at RT under argon. To this, 5-bromovaleronitrile (3.21 mL,4.45 g, 27.5 mmol, 2.2 eq.) was added in one portion and the reactionmixture was heated to reflux. Upon dissolution of S105, potassiumcarbonate (6.90 g, 49.9 mmol, 4 eq.) was added and the mixture wasstirred for 16 hr at reflux. The reaction mixture was allowed to cool toRT, and filtered through a fritted funnel. The product was re-dissolvedin DCM and deposited on silica gel and purified by column chromatography(Combi Flash Rf (120 g gold column). ¹H NMR (400 MHz, CDCl₃) δ 6.88 (d,J=8.7 Hz, 4H), 6.83 (d, J=3.6 Hz, 2H), 6.73 (d, J=3.7 Hz, 2H), 6.65 (d,J=8.7 Hz, 4H), 6.13 (s, 2H), 3.64 (m, 4H), 2.42 (t, J=6.6 Hz, 4H),1.89-1.76 (m, 8H), 1.41 (s, 18H).

Example 70 Synthesis of S1403,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(6-methoxy-2-(4-methoxyphenyl)benzofuran)

Synthesis of (E)-1-((1,2-dichlorovinyl)oxy)-3-methoxybenzene (89)

(89) was prepared on 1461 mmol scale (97%) yield according to protocol Ito give (E)-1-((1,2-dichlorovinyl)oxy)-3-methoxybenzene (19.5 g, 89mmol, 73.7% yield) as colorless oil.

Synthesis of 6-methoxy-2-(4-methoxyphenyl)benzofuran (90)

(90) was prepared on 28.4 mmol scale (62.2%) yield according to protocolJ, using olefin (89) to provide 6-methoxy-2-(4-methoxyphenyl)benzofuran(7.22 g, 28.4 mmol, 62.2% yield).

Synthesis of 3-bromo-6-methoxy-2-(4-methoxyphenyl)benzofuran (91)

91) was prepared on 21 mmol scale (74%) yield according to protocol F4.

Synthesis of S140

S140 was prepared on 0.74 mmol scale (16% yield) according to protocolH2. ¹H NMR (500 MHz, CDCl₃) δ 7.05 (d, J=8.7 Hz, 2H), 7.00 (d, J=8.7 Hz,4H), 6.81 (d, J=2.2 Hz, 2H), 6.68 (dd, J=8.7, 2.3 Hz, 2H), 6.45 (d,J=8.7 Hz, 4H), 3.83 (s, 6H), 3.63 (s, 6H).

Example 71 Synthesis of S1415,5′-(4,4′-(4,4′-(perfluorocyclopent-1-ene-1,2-diyl)bis(5′-tert-butyl-2,2′-bithiophene-5,4-diyl))bis(4,1-phenylene)bis(oxy))dipentanoicacid

Synthesis of S141

A suspension of S139 (7.3 g, 7.58 mmol) and KOH (8.76 g, 152 mmol) in awater ethanol mixture (1:1; 150 mL) was heated at reflux for two weeks.The solution was allowed to cool to RT, and the mixture was concentratedunder reduced pressure. The aqueous suspension was diluted with 200 mLof water, extracted with ether, and then acidified with 6 N HCl. a solidformed and was filtered off, washed with water and dried, then sonicatedin ether/hexanes and filtered. The yellow solid was dried under vacuumto give 5.8 g (76%) of pure S141. ¹H NMR (400 MHz, CDCl₃) δ 6.87 (d,J=8.4 Hz, 4H), 6.82 (d, J=3.4 Hz, 2H), 6.72 (d, J=3.4 Hz, 2H), 6.65 (d,J=8.4 Hz, 4H), 6.13 (s, 2H), 3.64 (s, 4H), 2.43 (d, J=6.6 Hz, 4H), 1.76(s, 8H), 1.40 (s, 18H).

Example 72 Synthesis of S1433,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(5,5″-di-tert-butyl-2,2′:5′,2″-terthiophene)

Synthesis of (2,2′-bithiophen)-5-yl-boronic acid (109)

In a flame-dried, 3-neck, 250 mL rbf, 2,2′-bithiophene (5.0 g, 30.1mmol) was dissolved in anhydrous THF (100 mL) and cooled to −78° C. (dryice/acetone). A solution of n-BuLi in hexanes (2.5 M, 12.6 mL, 31.6mmol) was added slowly over a period of ˜5 minutes. The reaction mixturewas allowed to stir at −78° C. for 15 minutes, and then trimethyl borate(10.1 mL, 90 mmol) was added dropwise over a period of 5 minutes. Thereaction was allowed to stir at −78° C. for 2 hours, then warm to RT andstir for a further 1 hour. The yellow reaction mixture was quenched bypouring it into a 10% HCl solution (250 mL). The mixture was extractedwith ether (2×100 mL) and the combined organic portions were washed withwater (500 mL), dried over MgSO₄, filtered and solvent removed by rotaryevaporation. The resulting yellow solid was washed with water, filteredand air dried to afford (109) (6.15 g, 97%). The material was used inthe next step without further purification.

Synthesis of 3-bromo-2,2′:5′,2″-terthiophene (111)

(111) was prepared on 21.6 mmol scale (37% yield) according to protocolD.

Synthesis of 3-bromo-5,5″-di-t-butyl-2,2′:5′,2″-terthiophene (112)

(112) was prepared on 3.66 mmol scale (98% yield) according to protocolE.

Synthesis of5,5″-di-tert-butyl-3-(perfluorocyclopent-1-en-1-yl)-2,2′:5′,2″-terthiophene(113)

In a flame-dried, 1 L rbf,3-bromo-5,5″-di-t-butyl-2,2′:5′,2″-terthiophene (112, 4 g, 9.10 mmol)was dissolved in anhydrous diethyl ether (400 mL) and cooled to −48° C.(dry ice/acetone). n-BuLi (2.5 M in hexanes, 1.5 mL, 3.82 mmol) wasadded dropwise over a period of 5 minutes. The resulting yellow solutionwas allowed to stir for 20 minutes, then octafluorocyclopentene (0.24mL, 1.82 mmol) was added in one portion. The reaction mixture warmed to−45° C. The reaction mixture was allowed to mix and slowly warm to 5°C., and then was poured into water (300 mL) and mixed well, thenacidified with 10% HCl (100 mL). The aqueous phase was separated andextracted with EtOAc (2×100 mL). The combined organics were washed withwater (500 mL), dried over MgSO₄, filtered and solvent removed by rotaryevaporation. The resulting dark orange oil was redissolved in chloroformand dry-loaded onto silica gel. Flash chromatography (hexanes) affordeda yellow oil, which was sonicated in methanol, filtered and air dried toafford 113 as a bright yellow, powdery solid (3.62 g, 72%).

Synthesis of S143

S143 was prepared on 1.90 mmol scale (42% yield) according to protocolH1. ¹H NMR (400 MHz, CDCl₃) δ 6.90 (d, J=3.7 Hz, 2H), 6.84 (d, J=3.7 Hz,2H), 6.71 (d, J=3.7 Hz, 2H), 6.55 (d, J=3.7 Hz, 2H), 6.27 (s, 2H), 1.39(s, 18H), 1.14 (d, J=6.1 Hz, 18H).

Example 73 Synthesis of S14433′-(perfluorocyclopent-1-ene-1,2-diyl)bis(6-methoxy-2-(5-methylthiophen-2-yl)benzofuran)

Synthesis of(Z)-2-(2-chloro-1-(3-methoxyphenoxy)vinyl)-5-methylthiophene (97)

(97) was prepared on 21.01 mmol scale (48.5%) yield according toprotocol J.

Synthesis of 6-methoxy-2-(5-methylthiophen-2-yl)benzofuran (98)

(Z)-2-(2-chloro-1-(3-methoxyphenoxy)vinyl)-5-methylthiophene (97) (4.7g, 16.74 mmol), Pd₂ dba₃ (0.178 g, 0.399 mmol),(oxybis(2,1-phenylene))bis(diphenylphosphine) (0.429 g, 0.797 mmol),cesium fluoride (7.27 g, 47.8 mmol) and cesium carbonate (15.58 g, 47.8mmol) were placed into a 250-mL three-neck rbf, sealed with a septum andpurged with argon for 20-30 minutes. 100 mL dioxane was added. Thesolution was vigorously stirred and brought to reflux for 18 hours andcooled. The layers were separated and the aqueous layer was extractedwith DCM once more. The combined organic layers were washed with brine,dried with anhydrous MgSO₄, filtered and concentrated. The product waspurified by column to provide (98) (3.38 g, 13.83 mmol, 87% yield).

Synthesis of 3-bromo-6-methoxy-2-(5-methylthiophen-2-yl)benzofuran (99)

(99) was prepared on 13.5 mmol scale (100% yield) according to protocolF4.

Synthesis of S144

S144 was prepared on 1.3 mmol scale (19% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.16 (d, J=8.7 Hz, 2H), 6.85 (d, J=2.2 Hz,2H), 6.75 (dd, J=8.8, 2.3 Hz, 2H), 6.72 (d, J=3.6 Hz, 2H), 6.27 (dd,J=3.5, 1.0 Hz, 2H), 3.83 (s, 6H), 2.19 (s, 6H).

Example 74 Synthesis of S1484′,4″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(3,4,4″,5,5″-pentamethyl-2,2′:5′,2-terthiophene)

Synthesis of4′,4″″-(perfluorocyclopent-1-ene-1,2-diyl)bis(3-bromo-4,4″,5,5″-tetramethyl-2,2′:5′,2″-terthiophene)(99a)

To a solution of S011 (0.56 g, 0.78 mmol) in dry DCM at −20° C. wasadded a solution of bromine (0.23 g, 1.437 mmol). The mixture wasstirred at RT for 5 h, washed with water and extracted with ether. Theorganic layer was separated and the solvent removed by rotaryevaporation. The residue was sonicated in ether/methanol (1:5), filteredand dried to afford a yellow solid (0.51 g, 76%).

Synthesis of S148

n-BuLi (2.5 M in hexane, 0.45 mL, 1.13 mmol) was added to a solution ofcompound 99a (0.41 g, 0.437 mmol) in THF (35 mL) at −30° C. After 10minutes, iodomethane (1 mL, 16.1 mmol) was added and the mixture wasstirred and warmed to RT, then stirred for another 30 min. and solventswere evaporated. The residue was washed with water and extracted withhexanes, dried over MgSO₄, and the solvent evaporated to give S148 as ayellow solid (0.341 g, 0.421 mmol, 97% crude yield). The chromophore waspurified by preparative TLC using hexanes/DCM (25%) as eluent. ¹H NMR(400 MHz, CDCl₃) δ 6.42 (s, 2H), 6.41 (s, 2H), 2.37 (s, 6H), 2.23 (s,6H), 2.10 (s, 6H), 2.06 (s, 6H), 1.91 (s, 6H).

Example 75 Synthesis of S1493′,3′″-(perfluorocyclopent-1-ene-1,2-diyl)bis(4,4″-dimethyl-2,2′:5′,2″-terthiophene)

Synthesis of 3′-bromo-4,4″-dimethyl-2,2′:5′,2″-terthiophene (124)

(124) was prepared on 29 mmol scale (66% yield) according to protocol D.

Synthesis of S149

S149 was prepared on 4.79 mmol scale (33% yield) according to protocolH1. ¹H NMR (400 MHz, CDCl₃) δ 6.88 (d, J=1.3 Hz, 2H), 6.81 (s, 2H), 6.72(s, 2H), 6.48 (d, J=1.3 Hz, 2H), 6.40 (s, 2H), 2.26 (s, 6H), 1.98 (s,6H).

Example 76 Synthesis of S1513,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)-6-methoxybenzofuran)

Synthesis of 2-(4-tert-butylphenyl)-6-methoxybenzofuran (125)

(125) was prepared on 13.0 mmol scale (52%) yield according to protocolJ. ¹H NMR (400 MHz, CDCl₃) δ 7.79-7.71 (m, 2H), 7.48-7.45 (m, 2H), 7.43(d, J=8.5 Hz, 1H), 7.08 (d, J=2.1 Hz, 1H), 6.91 (s, 1H), 6.87 (dd,J=8.5, 2.1 Hz, 1H), 3.88 (s, 3H), 1.36 (s, 9H).

Synthesis of 3-bromo-6-methoxy-2-(5-methylthiophen-2-yl)benzofuran (126)

(126) was prepared on 12.8 mmol scale (98% yield) according to protocolF4. ¹H NMR (400 MHz, CDCl₃) δ 8.11-8.02 (m, 2H), 7.54-7.48 (m, 2H), 7.40(d, J=8.6 Hz, 1H), 7.04 (d, J=2.1 Hz, 1H), 6.94 (dd, J=8.6, 2.1 Hz, 1H),3.88 (s, 3H), 1.37 (s, 9H).

Synthesis of S151

S151 was prepared on 0.73 mmol scale (14% yield) according to protocolH3. ¹H NMR (400 MHz, CDCl₃) δ 7.16-7.03 (m, 10H), 6.77 (d, J=2.2 Hz,2H), 6.65 (dd, J=8.8, 2.2 Hz, 2H), 3.78 (s, 6H), 1.16 (s, 18H).

Example 77 Synthesis of S1523,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(5′-(tert-butyl)-[2,2′-bithiophen]-5-yl)-6-methoxybenzofuran)

Synthesis of 5-(tert-butyl)-2,2′-bithiophene (114)

2,2′-bithiophene (10 g, 60.1 mmol) was dissolved in DCM (300 mL) and2-chloro-2-methylpropane (7.95 g, 72.2 mmol) was added. Aluminumchloride (8.82 g, 66.2 mmol) was added in one portion, and thecolourless solution turned a green/brown colour immediately. Thereaction mixture was stirred at room temperature for 30 minutes, thenwas poured into water (500 mL), mixed well and separated. The aqueousportion was extracted with DCM (200 mL) and the combined organics werewashed with brine (2×400 mL), dried over MgSO₄, filtered and solventremoved by rotary evaporation to afford a clear, green oil (13.3 g, 99%)that was used in the next step without further purification. ¹H NMR (400MHz, CDCl₃) δ 7.17 (dd, J=5.1, 1.1 Hz, 1H), 7.10 (dd, J=3.6, 1.1 Hz,1H), (dd, J=5.1, 3.6 Hz, 1H), 6.98 (d, J=3.6 Hz, 1H), 6.73 (d, J=3.7 Hz,1H), 1.40 (s, 9H).

Synthesis of (5′-(tert-butyl)-[2,2′-bithiophen]-5-yl)boronic acid (115)

In a flame-dried, 500 mL round bottom flask,5-(t-butyl)-2,2′-bithiophene (from U152-001, 13 g, 58.5 mmol) wasdissolved in anhydrous THF (200 mL) and the solution was cooled to −78°C. (dry ice/acetone). n-butyl lithium (2.5 M in hexanes, 25.7 mL, 64.3mmol) was added dropwise over a period of 10 minutes, and the resultinggreen solution was allowed to stir for 15 minutes. Trimethyl borate(19.6 mL, 175 mmol) was added dropwise over a period of 10 minutes, andthe resulting light yellow solution was stirred for 2 hours at −78° C.,then allowed to warm to room temperature and stirred for 1 hour. Thereaction was quenched by pouring it into 10% HCl (500 mL). The organicphase was separated and the aqueous phase extracted with ether (250 mL).The combined organics were washed with water (500 mL), dried over MgSO₄,filtered and solvent removed by rotary evaporation. The resulting greensolid was dried under vacuum to afford 15 g (96% yield), which was usedin the next step without further purification.

Synthesis of(Z)-5-(tert-butyl)-5′-(2-chloro-1-(3-methoxyphenoxy)vinyl)-2,2′-bithiophene(116)

In a 3 neck, 1 L round bottom flask,(5′-(t-butyl)-[2,2″-bithiophenene]-5-boronic acid (10.5 g, 39.4 mmol),(E)-1-((1,2-dichlorovinyl)oxy)-3-methoxybenzene (8.2 g, 37.6 mmol), weredissolved in THF (200 mL) and KOH (4.4 g, 79 mmol) in water (130 mL) wasadded. The reaction mixture was deoxygenated by bubbling argon throughthe solution for 1 hour. Tetrakis(triphenylphosphine)palladium (0) (2.17g, 1.9 mmol) was added and the reaction mixture was heated to reflux for18 hours. After cooling to room temperature, the mixture was poured intowater (500 mL), mixed well and separated. The aqueous portion wasextracted with ether (250 mL) and the combined organics were washed withwater (500 mL), dried over MgSO₄, filtered and solvent removed by rotaryevaporation. The resulting orange slurry was redissolved in DCM anddeposited on silica. Flash chromatography (combi-flash, hexanes)afforded a yellow, powdery solid (2.97 g, 20%). ¹H NMR (400 MHz, CDCl₃)δ 7.20-7.15 (m, 1H), 6.97 (d, J=3.8 Hz, 1H), 6.95 (d, J=3.7 Hz, 1H),6.91 (d, J=3.8 Hz, 1H), 6.71 (d, J=3.7 Hz, 1H), 6.62-6.57 (m, 3H), 6.34(s, 1H), 3.78 (s, 3H), 1.37 (s, 9H).

Synthesis of2-(5′-(tert-butyl)-[2,2′-bithiophen]-5-yl)-6-methoxybenzofuran (117)

(Z)-5-(tert-butyl)-5′-(2-chloro-1-(3-methoxyphenoxy)vinyl)-2,2′-bithiophene(2.9 g, 7.16 mmol) and DPEphos (0.19 g, 0.36 mmol) were dissolved inanhydrous 1,4-dioxane (40 mL). Cesium carbonate (7.0 g, 21.5 mmol) andcesium fluoride (3.3 g, 21.5 mmol) were added and the reaction mixturewas deoxygenated by bubbling argon through it for 1 hour.Tris(dibenzylideneacetone)dipalladium(0) (0.16 g, 0.18 mmol) was addedand the reaction mixture was heated to reflux for 20 hours. Aftercooling to room temperature, the reaction mixture was filtered, pouredinto water (250 mL), mixed well and separated. The aqueous portion wasextracted with ether (2×200 mL) and the combined organics were washedwith water (500 mL), dried over MgSO₄, filtered and solvent removed byrotary evaporation. The resulting brown solid was redissolved in DCM(250 mL) and deposited onto silica gel. Flash chromatography(combi-flash, hexanes) afforded a yellow, powdery solid, 1.53 g (58%).¹H NMR (600 MHz, CDCl₃) δ 7.40 (d, J=8.5 Hz, 1H), 7.29 (d, J=3.8 Hz,1H), 7.07 (d, J=3.8 Hz, 1H), 7.04 (d, J=1.4 Hz, 1H), 7.01 (d, J=3.6 Hz,1H), 6.86 (dd, J=8.5, 2.2 Hz, 1H), 6.76 (s, 1H), 6.75 (d, J=3.6 Hz, 1H),3.87 (s, 3H), 1.41 (s, 9H).

Synthesis of3-bromo-2-(5′-(tert-butyl)-[2,2′-bithiophen]-5-yl)-6-methoxybenzofuran(118)

(118) was prepared on 3.4 mmol scale (85% yield) according to protocolF4. ¹H NMR (600 MHz, CDCl₃) δ 7.64 (d, J=3.9 Hz, 1H), 7.36 (d, J=8.6 Hz,1H), 7.13 (d, J=3.9 Hz, 1H), 7.06 (d, J=3.6 Hz, 1H), 7.01 (d, J=2.0 Hz,1H), 6.93 (dd, J=8.6, 2.2 Hz, 1H), 6.76 (d, J=3.7 Hz, 1H), 3.88 (s, 3H),1.41 (s, 9H).

Synthesis of S152

S152 was prepared on 9.9 μmol scale (0.6% yield) according to protocolH2. ¹H NMR (400 MHz, CDCl₃) δ 7.20 (d, J=8.7 Hz, 1H), 6.80 (d, J=3.7 Hz,1H), 6.79 (d, J=3.8 Hz, 1H), 6.75 (d, J=2.2 Hz, 1H), 6.72 (d, J=3.7 Hz,1H), 6.64 (dd, J=8.8, 2.3 Hz, 1H), 6.55 (d, J=3.8 Hz, 1H), 3.61 (s, 3H),1.42 (s, 9H).

Example 78 Synthesis of S154

Synthesis of S154

LDA was made by addition of BuLi (0.9 mL, 2.25 mmol) to a solution ofdiisopropylamine (0.25 mL, 2.25 mmol) in THF (10 mL) at 0° C. withstirring for 10 min. S149 (0.365 g, 0.5 mmol) in THF (25 mL) was addedwith stirring at 0° C. for a further 10 min and cooled to −78° C.Oxirane (0.11 g, 2.5 mmol) was added, and stirred for 2 hr with gradualwarming to RT. The reaction was quenched with water (30 mL) and 10% HClsolution. Organics were extracted with ether (2×100 mL), washed withbrine (10 mL) and concentrated under reduced pressure. The crude productwas purified by column chromatography eluting with hexanes/ethylacetate, giving S154. Yield 50 mg (11%). ¹H NMR (400 MHz, CDCl₃) δ 6.81(s, 1H), 6.42 (s, 1H), 6.39 (s, 1H), 3.87 (t, J=5.8 Hz, 2H), 3.55 (t,J=7.1 Hz, 2H), 2.97 (t, J=5.8 Hz, 2H), 2.70 (t, J=7.1 Hz, 2H), 2.18 (s,3H), 1.96 (s, 3H), 1.88 (s, 4H).

Example 79 Synthesis of S155 3,3′-(perfluorocyclopent-1-ene-1,2diyl)bis(2-(3,4-dimethoxyphenyl)-6-methoxybenzofuran)

Synthesis of 2-(3,4-dimethoxyphenyl)-6-methoxybenzofuran (123)

(123) was prepared on 26.4 mmol scale (76.0%) yield according toprotocol J.

Synthesis of 3-bromo-2-(3,4-dimethoxyphenyl)-6-methoxybenzofuran (124)

(124) was prepared on 24.53 mmol scale (93%) yield according to protocolF4.

Synthesis of S155

In a 100-mL round bottom flask, containing3-bromo-2-(3,4-dimethoxyphenyl)-6-methoxybenzofuran (2 g, 5.51 mmol), amixture of anhydrous tert-butyl methyl ether (Ratio: 2, Volume: 40 ml)and THF (Ratio: 1.000, Volume: 20.00 ml) was cooled down to −78° C. inan acetone/dry ice bath. Butyllithium (2.313 ml, 5.78 mmol) was addedslowly followed by perfluorocyclopent-1-ene (0.369 ml, 2.75 mmol). Thereaction mixture was stirred for 1 hour, while the temperature wasincreasing gradually. The reaction was stopped by the addition of brine,and the mixture was transferred to a separation funnel. The organiclayer was extracted with ethyl acetate and dried over anhydrousmagnesium sulfate. The product was purified by chromatography columnusing Combi Flash Rf eluting with pure hexanes, then crystallized fromethanol to provide3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(3,4-dimethoxyphenyl)-6-methoxybenzofuran)(0.408 g, 0.551 mmol, 20% yield) as yellow solid. ¹H NMR (600 MHz,CDCl₃) δ 6.98 (d, J=8.6 Hz, 2H), 6.83 (d, J=2.1 Hz, 2H), 6.71 (dd,J=8.7, 2.2 Hz, 2H), 6.60 (d, J=8.2 Hz, 2H), 6.59 (s, 2H), 6.32 (d, J=8.2Hz, 2H), 3.84 (s, 6H), 3.82 (s, 6H), 3.70 (s, 6H).

Example 80 Synthesis of S158

To a solution of S170 (2 g, 2.56 mmol) in THF/ether (100 mL; 1:1) at−10-15° C. was added a solution of n-BuLi (2.4 mL, 5.63 mmol). Thereaction mixture turned brown, and was stirred for 15-20 min beforechlorotris(3-methoxypropyl)silane (compound (135); 1.6 g, 5.66 mmol) wasadded. The mixture was stirred at −10-15° C. for 1 h (TLC) and quenchedby methanol (6 mL) followed by water (6 mL). Saturated sodium chloride(30 mL) was then added. The mixture was extracted with ether, washedwith brine and concentrated under reduced pressure. CombiFlashchromatography (eluent hexanes/ethyl acetate; gradient to 40%) provided1.7 g (1.335 mmol; 52% yield) of S158. ¹H NMR (400 MHz, CDCl₃) δ 6.91(d, J=3.4 Hz, 2H), 6.86 (d, J=3.6 Hz, 2H), 6.72 (d, J=3.6 Hz, 2H), 6.69(d, J=3.4 Hz, 2H), 6.30 (s, 2H), 3.33-3.29 (m, 30H), 1.63-1.53 (m, 12H),1.41 (s, 18H), 0.77-0.69 (m, 12H).

Example 81 Synthesis of S1623,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)benzofuran-6-ol)

Synthesis of S162

In a one neck round bottom flask containing a solution of3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)-6-methoxybenzofuran)(1 g, 1.365 mmol) in anhydrous dichloromethane (Ratio: 1, Volume: 50 ml)at room temperature was added dropwise tribromoborane (1.8 ml, 18.68mmol). The reaction mixture was stirred at reflux for 2 hours. The TLCafter 2 hours showed that all the starting material was consumed. Thereaction was quenched with methanol (vigorous reaction). The crude waswashed with an aqueous solution of 10% HCl, extracted with DCM, thendried over anhydrous magnesium sulfate. The solid obtained was depositedon silica gel and purified by chromatography column using CombiFlash Rfeluting with pure DCM to obtain the product3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)benzofuran-6-ol)(0.96 g, 1.362 mmol, 100% yield) as fluffy yellow solid. ¹H NMR (500MHz, CDCl₃) δ 7.1 (AB, J=8.4 Hz, 8H), 7.06 (m, 2H), 6.73 (d, J=2.1 Hz,2H), 6.54 (dd, J=8.6, 2.2 Hz, 2H), 4.77 (s, 2H), 1.18 (s, 18H).

Example 82 Synthesis of S1613,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)-6-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)benzofuran)

Synthesis of S161

In a one neck round bottomed flask,3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)benzofuran-6-ol)(0.9 g, 1.277 mmol) was dissolved in Acetonitrile (Ratio: 1, Volume: 50ml) at room temperature under argon, then potassium carbonate (0.706 g,5.11 mmol) was added. To the resulting suspension was added a solutionof 2-(2-(2-ethoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (103)(1.061 g, 3.19 mmol) in anhydrous acetonitrile in one portion and themixture was stirred overnight at reflux. The reaction mixture wasallowed to cool down to room temperature, poured into a separationfunnel containing water. The organic layer was extracted with ethylacetate and dried over magnesium sulfate. The filtrate was concentratedto provide the crude product as red/brown oil. The crude was loaded assolution into the chromatography column and purified using CombiFlash Rf(starting with 10% ethyl acetate in hexanes until 40% ethyl acetate inhexanes) to provide the product3,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)-6-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)benzofuran)(1.2 g, 1.171 mmol, 92% yield) as thick red oil (dark state). ¹H NMR(400 MHz, CDCl₃) δ 7.12 (d, J=8.5 Hz, 4H), 7.07 (m, 6H), 6.78 (d, J=2.1Hz, 2H), 6.66 (dd, J=8.8, 2.2 Hz, 2H), 4.08 (t, J=4.68 Hz, 4H), 3.85 (t,J=5.20 Hz, 4H), 3.74 (m, 4H), 3.72-3.63 (m, 8H), 3.60 (m, 4H), 3.53 (q,J=7.0 Hz, 4H), 1.21 (t, J=7.0 Hz, 6H), 1.16 (s, 18H).

Example 83 Synthesis of S1637,7′-(perfluorocyclopent-1-ene-1,2-diyl)bis(6-(4-(tert-butyl)phenyl)-[1,3]dioxolo[4,5-f]benzofuran)

Synthesis of (E)-5-((1,2-dichlorovinyl)oxy)benzo[d][1,3]dioxole (125)

(125) was prepared on 644 mmol scale (89%) yield according to protocolI.

Synthesis of 6-(4-(tert-butyl)phenyl)-[1,3]dioxolo[4,5-f]benzofuran(126)

(126) was prepared on 43.1 mmol scale (68.2%) overall yield according toprotocol J. (126) was obtained as a mixture of two isomers (41:59 ratioof product:by-product according to H NMR spectrum).

Synthesis of7-bromo-6-(4-(tert-butyl)phenyl)-[1,3]dioxolo[4,5-f]benzofuran (127)

(127) was prepared on 38.59 mmol scale (84.0%) overall yield accordingto protocol F1. (127) was obtained as a mixture of two isomers (42:58ratio) according to H NMR spectrum). The two isomers were separated bymultiple chromatography column. In total, it was obtained:8-bromo-7-(4-(tert-butyl)phenyl)-[1,3]dioxolo[4,5-e]benzofuran (8.4 g,22.51 mmol, 49.0% yield) and7-bromo-6-(4-(tert-butyl)phenyl)-[1,3]dioxolo[4,5-f]benzofuran (6.0 g,16.08 mmol, 35.0% yield).

Synthesis of S163

S163 was prepared on 2.01 mmol scale (25.0%) overall yield according toprotocol H3. A side product (131) was also generated (see Scheme 95 forstructure). ¹H NMR (400 MHz, CDCl₃) δ 7.14-7.09 (A₂, 8H), 6.73 (s, 2H),6.62 (s, 2H), 5.93 (s, 4H), 1.20 (s, 18H).

Example 84 Synthesis of S1643,3′-(perfluorocyclopent-1-ene-1,2-diyl)bis(2-(4-(tert-butyl)phenyl)-5,6-dimethoxybenzofuran)

Synthesis of (E)-4-((1,2-dichlorovinyl)oxy)-1,2-dimethoxybenzene (128)

(128) was prepared on 162 mmol scale (100%) yield according to protocolI.

Synthesis of 2-(4-(tert-butyl)phenyl)-5,6-dimethoxybenzofuran (129)

(129) was prepared on 19.33 mmol scale (40.1%) yield according toprotocol J.

Synthesis of 3-bromo-2-(4-(tert-butyl)phenyl)-5,6-dimethoxybenzofuran(130)

(130) was prepared on 19.27 mmol scale (100%) yield according toprotocol F2.

Synthesis of S164

S164 was prepared on 2.65 mmol scale (27.5%) yield according to protocolH3. A side product (139) was also generated (see Scheme 96 forstructure). ¹H NMR (400 MHz, CDCl₃) δ 7.13-7.05 (A₂, 8H), 6.81 (s, 2H),6.75 (s, 2H), 3.86 (s, 6H), 3.76 (s, 6H), 1.12 (s, 18H).

Example 85 Other Compounds

Other compounds according to Formula I-X are illustrated in Table 8.

  U008

  U009

  U010

  U016

  U018

  U021

  U022

  U023

  U025

  U028

  U029

  U030

  U031

  U041

  U045

  U051

  U058

  U061

  U062

  U069

  U070

  U071

  U072

  U076

  U077

  U078

  U080

  U081

  U082

  U093

  U099

  U100

  U101

  U102

  U107

  U114

  U117

  U120

  U121

  U122

  U123

  U125

  U126

  U127

  U129

  U130

  U131

  U132

  U133

  U134

  U136

  U142

  U145

  U146

  U147

  U150

  U152

  U153

  U156

  U157

  U159

  U160

  U165

  S033

  S075

Example 86 Synthesis of S191

A solution of (2) (0.67 g; 1.53 mmol) in anhydrous diethyl ether (15 mL)was cooled to −78° C. n-Butyl lithium (0.67 mL; 1.66 mmol; 2.5 M inhexane) was added. The mixture was stirred at this temperature for 10min. A solution of (139) (0.62 g; 1.28 mmol) was added as a solution inether (10 ml) over 5 min. The reaction mixture was stirred for 10 minand allowed to warm to room temperature with stirring overnight. Thereaction was quenched by addition of 10% aqueous HCl (5 mL), the organicfraction separated, and the product isolated using preparative TLC(yield: 0.14 g)

Example 87 Synthesis of S193

A solution of (1) (0.82 g; 2.5 mmol) in anhydrous diethyl ether (15 mL)was cooled to −78° C. n-Butyl lithium (1.05 mL; 2.63 mmol; 2.5 M inhexane) was added. The mixture was stirred for 10 min, and a solution of(139) (0.628 g; 1.25 mmol) ether (10 ml) was added over 5 min. Thereaction mixture was stirred for 15 min and quenched by addition of 10%HCl (5 mL). The product was obtained by column purification. Yield 0.44g (48.2%).

Example 88 PSS and Light Composition

The difference in PSS as a function of light source type wasinvestigated. The light sources included direct sunlight (filteredthrough window glass) and interior lighting. Irradiance information andspectral profiles of light sources are provided in Table 9 and FIG. 2,respectively. Six compounds (2×10⁻⁴ M solutions of S096, S094, S079,S044, S042 and S035 in triglyme) were investigated and compared forperformance on the basis of maximum difference in darkening abilitybetween sunlight and interior lighting conditions. Darkening ability isindicated by the absorbance at λmax in the visible light spectrum forthe ring-closed isomer of the chromophore.

TABLE 9 Description of Lighting Conditions and Intensity Full SpectrumApproximate Temperature Light Intensity Condition Time of Day (° C.)(W/m²) Photostationary State (FIG. 3) A—Interior lighting only¹ 17:1522.2 29 B—Sunlight + Interior 16:20 24.6 73 Lights² C—Sunlight³ 15:0524.7 114  Time to Reach Photostationary State (FIG. 4) A—Interiorlighting only¹ 12:45 24.1 29 B—Sunlight + Interior 12:03 23.6 40-43Lights² C—Sunlight³ 12:14 22.4 32-70 ¹Samples were irradiated with thelight from halogen bulbs (Philips Master Line 75 Watt Flood) in a labwhere all window shutters were tightly closed to block out sunlight.²Samples were irradiated in the same lab described above but with theshutters open to allow sunlight to enter the lab. Distance betweensample and window was 300 cm. ³Samples were irradiated in the same labdescribed above but with the shutters open to allow sunlight to enterthe lab. Distance between sample and window was 20 cm.

Samples were first irradiated with sunlight at a distance 20 cm from thewindow, which resulted in the darkest colouration of the samples.Samples were then moved away from the window (300 cm from window, withinterior lighting on) to alter the light composition by reducing thesunlight component. This resulted in the fading of samples due tovisible-light induced photochromism (samples were thermally stable atambient temperature and did not alter coloration over a period ofseveral hours wen protected from light sources) as shown in FIG. 3.Finally, samples were again irradiated to the darkest state undersunlight conditions (20 cm from window) and then subjected to interiorlighting conditions only (sunlight blocked out with blinds), allowingthe samples to fade to a lower PSS specific to these lighting conditionsas shown in FIG. 3.

Compounds S094 and S042 demonstrated the greatest change in degree ofcoloration in response to variation in the light source. Sampledarkening times were less than one minute, while sample photofadingtimes ranged as high as 20 minutes. FIG. 4 shows the time and absorbancefor sunlight+interior light, and interior light alone for S094. Thisexperiment illustrates the differing ‘sensitivity’ and effect on PSS ofselected compounds with respect to the composition of the light(sunlight having a UV component, which is absent in interior light, asillustrated in FIG. 2).

OTHER EMBODIMENTS

It is contemplated that any embodiment discussed in this specificationcan be implemented or combined with respect to any other embodiment,method, composition or aspect, and vice versa. Figures are not drawn toscale unless otherwise indicated.

The present invention has been described with regard to one or moreembodiments. However, it will be apparent to persons skilled in the artthat a number of variations and modifications can be made withoutdeparting from the scope of the invention as defined in the claims.Therefore, although various embodiments of the invention are disclosedherein, many adaptations and modifications may be made within the scopeof the invention in accordance with the common general knowledge ofthose skilled in this art. Such modifications include the substitutionof known equivalents for any aspect of the invention in order to achievethe same result in substantially the same way. Numeric ranges areinclusive of the numbers defining the range. In the specification, theword “comprising” is used as an open-ended term, substantiallyequivalent to the phrase “including, but not limited to,” and the word“comprises” has a corresponding meaning. As used herein, the singularforms “a”, “an” and “the” include plural referents unless the contextclearly dictates otherwise. Citation of references herein shall not beconstrued as an admission that such references are prior art to thepresent invention, nor as any admission as to the contents or date ofthe references. All publications are incorporated herein by reference asif each individual publication was specifically and individuallyindicated to be incorporated by reference herein and as though fully setforth herein. The invention includes all embodiments and variationssubstantially as hereinbefore described and with reference to theexamples and drawings.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of ordinary skillin the art to which this invention belongs. If a definition set forth inthis section is contrary to or otherwise inconsistent with a definitionset forth in the documents that are herein incorporated by reference,the definition set forth herein prevails over the definition that isincorporated herein by reference.

What is claimed is:
 1. A compound according to Formula VIIA/B, reversibly convertible under photochromic and electrochromic conditions between a ring-open isomer A and a ring-closed isomer B:

Z is O; each R₁ is independently selected from the group consisting of H, or halo; each R₂ is independently selected from the group consisting of H, halo, a polymer backbone, alkyl or aryl; or, when both R₂ together form —CH═CH— and form part of a polymer backbone; each R₄ is

X is N, O or S; and each R_(7a), R_(7b), R_(7c); and each R_(9a), R_(9b), R_(9c), R_(9d), R_(9e) is independently selected from a group consisting of: H, Cl, Br, F, —CF₃, —CN, —NO₂, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated or unsaturated alkyl that is linear or branched with 5-12 carbons, —Si(R₁₁)₃, thiophene, substituted thiophene, benzyl, substituted benzyl, —CH₂—CH₂—, —CH═CH—, —CH═CH₂, —OCH₃, —COH, —OH, —CO₂H, —COCH₃, —C(CH₃)₂OH, —Si(CH₃)₃, —CH₂CH₂OCH₃, —CH₂CH₂OH, —N(CH₃)₂, —CO₂CH₃, —OCH₂OCH₃, —SO₂CH₃, —OCH₂C(CH₃)₃, —OCH₂CH(CH₃)₂, —OC(CH₃)₃, —OCH═CH₂, —O(CH₂)₄CN, —O(CH₂)₄OH, —O(CH₂)₃OH, —C(CH₃)₂OH, —OCH₂)₂OCH₃,

n and m are independently any integer from 0 to 20; R₁₁ is independently selected from the group comprising R or —O—R, and wherein R is linear or branched, non-aromatic monocyclic or polycyclic, substituted or unsubstituted alkyl group of 1 to 20 carbons; or R is a heteroalkyl group comprising one or more of O, S, N or Si; or each R is a saturated or unsaturated alkyl that is linear or branched with 1-12 carbons; or each R is a substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl; R_(10a) is selected from a group consisting of an electron donating group (EDG), an electron withdrawing group (EWG), —OCH₃, —CN, —OH, H,

R_(10b) is selected from a group consisting of an electron donating group (EDG), an electron withdrawing group (EWG), —OCH₃, —CN, —OH, H,

R_(10c) is selected from a group consisting of an electron donating group (EDG), an electron withdrawing group (EWG), —OCH₃, —CN, —OH,

R_(10d) is selected from a group consisting of, an electron donating group (EDG), an electron withdrawing group (EWG), —OCH₃, —CN, —OH, H,

or R_(10b) and R_(10c) are each O and joined by —CH₂— to form a 5-membered ring.
 2. The compound according to claim 1 wherein both R₂ are —CH═CH— and form part of a polymer backbone.
 3. The compound according to claim 1 wherein R₄ is

and X is S.
 4. The compound according to claim 1 wherein R₄ is


5. The compound according to claim 1 wherein: a. the electron donating group is selected from a group consisting of —OH, OR, NH₂, NHR, NR₂, electron-rich heteroaryl groups, electron-rich substituted aryl groups, —O⁻, amine, alcohol, ether, thioether, alkyl and carbamate; and b. the electron withdrawing group is selected from a group consisting of halogen, electron-poor heteroaryl groups, electron-poor substituted aryl groups, —NO₂, —⁺NR₃, —⁺NH₃, —SO₃H, —CN, CF₃, aldehyde, ester, carboxylic acid, carbonyl, carbonyl chloride and amide.
 6. The compound according to claim 1 wherein R_(9a), R_(9b), R_(9c), R_(9d) and R_(9e) are each independently selected from a group consisting of H, Cl, Br, F, —CF₃, —CN, —NO₂, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl and tert-butyl; and wherein R_(10a) is selected from a group consisting of —OCH₃, —CN, —OH, H,

R_(10b) is selected from a group consisting of —OCH₃, —CN, —OH, H,

R_(10c) is selected from a group consisting of —OCH₃, —CN, —OH,

and R_(10d) is selected from a group consisting of —OCH₃, —CN, —OH, H,


7. The compound according to claim 4 wherein R_(9e) is tert-butyl.
 8. The compound according to claim 1 wherein R_(9a), R_(9b), R_(9d) and R_(9e) are H.
 9. The compound according to claim 1 wherein one or more of R_(10a), R_(10b), R_(10c) and R_(10d) are —OCH₃.
 10. The compound according to claim 1 wherein R_(10c) is


11. The compound according to claim 1 wherein R is substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl.
 12. The compound according to claim 1, selected from the group consisting of


13. A compound according to Formula IA/IB, reversibly convertible under photochromic and electrochromic conditions between a ring-open isomer A and a ring-closed isomer B:

wherein Z is N, O or S; each R₁ is independently selected from the group consisting of H, or halo; each R₂ is independently selected from the group consisting of H, halo, a polymer backbone, alkyl or aryl; or, when both R₂ together form —CH═CH— and form part of a polymer backbone; each R₃ is

both R₄ are

or both R₄ are

and R_(6a) and R_(7a) are not methyl; X=S; each R₅ is H; each R_(6a), R_(6b), R_(6c); each R_(7a), R_(7b), R_(7c); and each R_(9a), R_(9b), R_(9c), R_(9d), R_(9e) is independently selected from a group comprising: H, Cl, Br, F, —CF₃, —CN, —NO₂, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated or unsaturated alkyl that is linear or branched with 5-12 carbons, —Si(R₁₁)₃, thiophene, substituted thiophene, benzyl, substituted benzyl, —CH₂—CH₂—, —CH═CH—, —CH═CH₂, —OCH₃, —COH, —OH, —CO₂H, —COCH₃, —C(CH₃)₂OH, —Si(CH₃)₃, —CH₂CH₂OCH₃, —CH₂CH₂OH, —N(CH₃)₂, —CO₂CH₃, —OCH₂OCH₃, —SO₂CH₃, —OCH₂C(CH₃)₃, —OCH₂CH(CH₃)₂, —OC(CH₃)₃, —OCH—CH₂, —O(CH₂)₄CN, —O(CH₂)₄OH, —O(CH₂)₃OH, —C(CH₃)₂OH, —O(CH₂)₂OCH₃, —O(CH₂)₄CN, —O(CH₂)₄COOH

or where R_(6a) and R_(6b) are each —CH═CH— and joined to form an unsaturated ring; wherein n and m are independently any integer from 0 to 20; and wherein R₁₁ is independently selected from the group comprising R or —O—R, and wherein R is linear or branched, non-aromatic monocyclic or polycyclic, substituted or unsubstituted alkyl group of 1 to 20 carbons; or R is a heteroalkyl group comprising one or more of O, S, N or Si; or each R is a saturated or unsaturated alkyl that is linear or branched with 1-12 carbons; or each R is a substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl; and at least one of R_(6a), R_(6b), R_(6c) is not H; at least one of R_(7a), R_(7b), R_(7c) is not H; and at least one of R_(9a), R_(9b), R_(9c), R_(9d), R_(9e) is not H.
 14. The compound according to claim 13 wherein both R₂ are —CH═CH— and form part of a polymer backbone.
 15. The compound according to claim 13 wherein: each R_(6a) is independently selected from a group consisting of H, Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R₁₁)₃, thiophene, substituted thiophene, —CO₂H, —COCH₃, —Si(CH₃)₃; each R_(6b) is independently selected from a group consisting of H, Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R₁₁)₃, thiophene, substituted thiophene, —CO₂H, —COCH₃, —Si(CH₃)₃; each R_(6c) is independently selected from a group consisting of H, Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R₁₁)₃, thiophene, substituted thiophene, —CO₂H, —COCH₃, —Si(CH₃)₃; R₁₁ is R, and R is a heteroalkyl group of from 1 to 10 carbons, comprising one or more of O, S; and at least one of R_(6a), R_(6b), R_(6c) is not H.
 16. The compound according to claim 13 wherein the substituted thiophene of R_(6a), R_(6b) or R_(6c) is


17. The compound according to claim 13 wherein R_(6a) is selected from a group consisting of Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R₁₁)₃, thiophene, substituted thiophene, methyl thiophene, —CO₂H, —COCH₃, —Si(CH₃)₃, and wherein R₁₁ is R, and R is a heteroalkyl group of from 1 to 10 carbons, comprising one or more O, S; R_(6b) is H or CH₃; and R_(6c) is H or CH₃.
 18. The compound according to claim 13 wherein R₁₁ is —CH₃ or —(CH₂)₁₋₁₀—OCH₃.
 19. The compound according to claim 13 wherein both R₄ are


20. The compound according to claim 13 wherein both R₄ are


21. The compound according to claim 13 wherein R_(9c) is —OCH₃, —OH, —O(CH₂)₄CN, —O(CH₂)₄COOH, —O(CH₂)₃OH,


22. The compound according to claim 13 selected from the group consisting of:


23. The compound according to claim 13 wherein R_(7a) is H, Cl, Br, F, —CF₃, —CN, —NO₂, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated or unsaturated alkyl that is linear or branched with 5-12 carbons, —Si(R₁₁)₃, thiophene, substituted thiophene, benzyl, substituted benzyl, —CH₂—CH₂—, —CH═CH—, —CH═CH₂, —OCH₃, —COH, —OH, —CO₂H, —COCH₃, —C(CH₃)₂OH, —Si(CH₃)₃, —CH₂CH₂OCH₃, —CH₂CH₂OH, —N(CH₃)₂, —CO₂CH₃, —OCH₂OCH₃, —SO₂CH₃, —OCH₂C(CH₃)₃, —OCH₂CH(CH₃)₂, —OC(CH₃)₃, —OCH—CH₂, —O(CH₂)₄CN, —O(CH₂)₄OH, —O(CH₂)₃OH, —C(CH₃)₂OH, —O(CH₂)₂OCH₃, —O(CH₂)₄CN, —O(CH₂)₄COOH,


24. The compound according to claim 23 wherein R₁₁ is —CH₃ or —(CH₂)₁₋₁₀—OCH₃.
 25. The compound according to claim 13 wherein R is substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl. 